Anti-smudge and anti-graffiti compositions

ABSTRACT

Polyurethane-based and epoxy-based coating compositions are described that provide coatings and adhesives that are clear, amphiphobic and durable. Both water and hexadecane readily slide off these surfaces without leaving a residue. Coatings with thicknesses ranging from about 10 nm to about 10 μm exhibited excellent transmittance properties. Such films exhibited durability against abrasion, ink-resistance, anti-graffiti, anti-fingerprint, and strong adhesion to glass surfaces. The coatings are applicable to electronic devices, fabrics, glass, etc. to prepare optically clear, stain-resistant, and smudge-resistant surfaces.

FIELD OF THE INVENTION

The field of the invention is coatings and adhesives. More specifically,the field is coatings that are thick enough to endure wear, applicableto many different substrates, and repel water and oil.

BACKGROUND OF THE INVENTION

Screens and surfaces of cell phones, tablets, and other hand-heldelectronic devices are susceptible to fingerprints and smudgedeposition. The windows of high-rise buildings can develop stains due todust deposition from rain or ice droplets. Automobile bodies andwindshields become dirty from mud and dust. Such deposits affect theaesthetic appeal of objects and decrease our enjoyment. When thesedeposits accumulate on the screens of hand-held electronic devices orwindows and windshields, they deteriorate display quality and diminishone's ability to use the device or to operate the vehicle. All theseissues can be alleviated with anti-smudge coatings that are alsooptically clear and durable.

Currently, there are no durable amphiphobic (oil- and water-repellent)and optically-clear coatings on the market for hand-held electronicdevices, windshields, or the windows of high-rises.Perfluoropolyether-silane-based liquids are sold as coatings forhand-held electronic devices. These coatings are of limited use becausethey are not wear resistant.

A typical polyurethane or epoxy coating is fairly water repellent, butdoes not have oil repellent properties. Accordingly, neitherpolyurethane nor epoxy is an amphiphobic coating. Polyurethanes areproduced by reacting an isocyanate containing two or more isocyanategroups per molecule (R—(N═C═O)n with n ≥2) with a polyol containing onaverage two or more hydroxy groups per molecule (R′—(OH)n with n ≥2),optionally in the presence of a catalyst, see Scheme 1. The propertiesof polyurethane are greatly influenced by the types of isocyanates andpolyols from which it was made. Epoxy coatings are produced by reactinga resin with a hardener (also called an activator), see FIG. 10.

Two-component polyurethane coatings have two mutually reactivecomponents that are stored separately. One component bears hydroxylgroups. The other component bears isocyanate groups. The two differentcomponents are typically stored in pre-polymer or oligomeric form toreduce vapour pressures for safety and toxicity reasons. A pre-polymeris a medium molecular weight species, between a molecule and a polymer.Pre-polymers have a lower vapour pressure than its corresponding lowmolecular weight molecular reactive components (Gite, V. et al. Prog.Org. Coat. 2010, 68, 307). When the two different components are mixedtogether, the hydroxyl groups react with the isocyanate groups toproduce a crosslinked PU film or coating, as shown below in arepresentative example of polyurethane synthesis. For convenience, adiisocyanate and a diol are shown below. When crosslinked polyurethaneis desired then diisocyanate is used with a polyol crosslinking agent,which has three or more functionalities per molecule to enable formationof fully branched/crosslinked networks. PU can be applied to a widerange of substrates. However, traditional PU coatings do not possessanti-smudge properties.

Epoxy coatings typically have two mutually reactive components that arestored separately. One component bears epoxide moieties. The othercomponent bears hardeners that comprise hydroxyl, amino, amine, imine,anhydride, or carboxyl groups. When the two different components aremixed together, they produce a crosslinked film or coating. Epoxycoatings/adhesives can be applied to a wide range of substrates.However, traditional epoxy coatings do not possess anti-smudgeproperties.

There is a need for amphiphobic (e.g., anti-smudge) coatings that areoptically clear and durable.

SUMMARY OF THE INVENTION

An aspect of the invention provides a composition including: a majorcomponent that is a polymer that is capable of crosslinking at multiplesites to form a solid material, or a major component that is anengineering plastic; and a minor component that is a polymer having afirst end that is capable of binding to the major component and having asecond end that remains unbound; wherein the composition is adapted tobe applied to a substrate and dried and/or cured to form a coating onthe substrate, such that: the second end of at least a portion of theminor component is located at a surface of the coating; and the coatingis amphiphobic.

In an embodiment of this aspect, the minor component polymer has a glasstransition temperature (Tg) in the range of about −160° C. to 25° C. Inanother embodiment of this aspect, the major component comprisespolyurethane, epoxy resin, Nylon 6, Nylon 6-6, poly(acrylate),polyamide, poly(butylene terephthalate), polycarbonate,poly(etherketone), poly(etheretherketone), polyethylene, polyethyleneterephthalate), polyimide, poly(methacrylate), poly(oxymethylene),poly(phenylene sulfide), poly(phenylene oxide), polypropylene(isotactic), polysulphone, polystyrene, or a combination thereof. In anembodiment of this aspect, the coating is substantially transparent. Inan embodiment of this aspect, the major component comprises polyurethaneor epoxy resin. In an embodiment of this aspect, the minor componentcomprises about 0.1 wt % to about 40 wt % of the composition. In anembodiment of this aspect, the minor component polymer has a Tg of about25° C. or less and is selected from perfluoropolyether (PFPE),polysiloxane, poly (ethylene glycol) methyl ether (PEO), polyisobutylene(PIB), polybutadiene (PB), or a polymeric form of: ethylene (atactic),1-butene, ethylene, cis-isoprene, trans-isoprene, 1-octene, propylene,vinyl propionate, vinylidene chloride, vinylidene fluoride,cis-chlorobutadiene, trans-chlorobutadiene, benzyl acrylate, butylacrylate, sec-butyl acrylate, 2-cyanoethyl acrylate, cyclohexylacrylate, dodecyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate,isobutyl acrylate, 2,2,2-trifluoroethyl acrylate, 2-ethoxyethylacrylate, isopropyl acrylate (isotactic), benzyl methacrylate,diethylaminoethyl methacrylate, dodecyl methacrylate, 2-ethylhexylmethacrylate, hexadecyl methacrylate, hexyl methacrylate, octadecylmethacrylate, octyl methacrylate, propyl vinyl ether, methyl vinylether, methyl glycidyl ether, isobutyl vinyl ether, ethyl vinyl ether,2-ethylhexyl vinyl ether, dodecyl vinyl ether, butyl vinyl ether, butylglydicyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide,tetrahydrofuran, 1,2-epoxybutane, 1,2-epoxydecane, 1,2-epoxyoctane,epibromohydrin, epichlorohydrin, trimethylene oxide, epibromohydrin,epichlorohydrin, tetramethylene terephthalate, tetramethylene adipate,ethylene malonate, ethylene adipate, ϵ-caprolactone, dimethylsiloxane,methylphenylsiloxane, formaldehyde,ethylene-trans-1,4-cyclohexyldicarboxylate, acetaldehyde, orpoly(l-glycidyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide)(“polyGBIMTFSI”); or a phosphazene polymer

-   -   where R₁ and R₂ are CH₃, C₆H₅, OCH₃, OC₆H₅, NR₂, Cl, Br, F,        OCH₂CF₃, or OCH₂C₆H₅;    -   or any combination thereof.

In further embodiments of this aspect, compositions further comprisingbiocide, embedded particles selected from silica, titanium dioxide,diatomaceous earth, alumina, TiO₂, and/or a pigment.

In some embodiments of this aspect, the minor component is a graftcopolymer of formula (1) or a block copolymer of formula (2):

where FS is a moiety comprising PFPE, polysiloxane, PEO, PIB, PB, apolymer whose Tg is 25° C. or less as described above, or anycombination thereof; R is a moiety that comprises a hydroxyl, amine(NH₂), imine (NH), carboxyl, glycidyl, isocyanato, or an anhydridefunctional group that is protected or unprotected; Mi is a monomerselected from styrene, acrylate, methacrylate, vinyl esters, acrylicacids, methacrylic acids, amine-bearing monomers, anhydride-bearingmonomers, polyimine/polyamine, or polycarboxylic acid/polyanhydride; xis percentage of FS moieties and is from about 0.1% to about 40%; y ispercentage of R moieties and is from about 1% to about 90%; n is numberof repeat units.

In certain embodiments of this aspect, FS further comprises at least onemoiety that links FS to R or Mi of the copolymer. In some embodiments ofthis aspect, the PFPE moiety is Demnum, Fluorlink link Diol, Fomblin Z,Krytox®, or Aflunox. In certain embodiments of this aspect, the minorcomponent comprises: PFPE-b-P(HEMA-S-MMA); PDMS-b-[HEMA-S-MMA];PDMS-b-PGMA; Polyol-g-PIB; Polyol-g-PB;P(S-MMA-MAA-BMA-IBMA-VP-EGEMA-HEMA)-g-PFPE; P(TFEMA-co-HEMA)-g-PFPE;P(S-MMA-MAA-BMA-IBMA-VE-EGEMA-HEMA)-g-PDMS; P(S-alt-MA)-g-PEO₇₅₀;P(S-alt-MA)-g-PEO₂₀₀₀; P(S-alt-MA)-g-PEO₅₀₀₀; PFPE-b-P(HEMA-S-MMA);PDMS-b-[HEMA-S-MMA]; PDMS-b-PGMA; Polyol-g-PIB; Polyol-g-PB; or anycombination thereof. In some embodiments of this aspect, FS comprisespolydimethylsiloxane. In certain embodiments of this aspect, FScomprises: CH₂═CH—CO₂-polysiloxane; CH₂═CH—CO₂-PDMS;CH₂═C(CH₃)—CO₂-polysiloxane; CH₂═C(CH₃)—CO₂-PDMS; CH₂═CH—CO₂-PFPE;CH₂═CH—CO₂-Krytox; CH₂═C(CH₃)—CO₂-PFPE; CH₂═C(CH₃)—CO₂-Krytox; orCH₂═C(CH₃)COOCH₂CH₂OOCCF(CF₃)[CF₂—CF(CF₃)O]_(i)CF₃. In other embodimentsof this aspect, FS comprises a PFPE moiety that comprises a C₁₀ to C₂₀₀₀perfluoro polyether moiety. In certain embodiments of this aspect, theminor component comprises polysiloxane, PFPE, PEO, or PIB, or anycombination thereof; wherein the polysiloxane, PFPE, PEO, PIB, or anycombination thereof is grafted to a polymer, wherein the polymer isselected from polyacrylate, polymethacrylate, polyacrylic acid,polymethacrylic acid, polystyrene, polyvinyl ester, polyimine/polyamine,polycarboxylic acid/polyanhydride, or any combination thereof. Incertain embodiments of this aspect, the FS moiety comprises:polyacrylate-g-polysiloxane; polymethacrylate-g-polysiloxane;poly(acrylic acid)-g-polysiloxane; poly(methacrylicacid)-g-polysiloxane; polystyrene-g-polysiloxane; poly(vinylester)-g-polysiloxane; polyacrylate-g-PFPE; polymethacrylate-g-PFPE;poly(acrylic acid)-g-PFPE; poly(methacrylic acid)-g-PFPE;polystyrene-g-PFPE; polyvinyl ester-g-PFPE; PEI-g-PDMS;P(S-alt-MA)-g-PDMS; polyacrylate-b-polysiloxane;polymethacrylate-b-polysiloxane; polyacrylic acid-b-polysiloxane;polymethacrylic acid-b-polysiloxane; polystyrene-b-polysiloxane;polyvinyl ester-b-polysiloxane; polyacrylate-b-PFPE;polymethacrylate-b-PFPE; poly(acrylic acid)-b-PFPE; poly(methacrylicacid)-b-PFPE; polystyrene-b-PFPE; poly(vinyl ester)-b-PFPE; orPDMS-b-PGMA.

Another aspect of the invention provides a polyurethane-based coatingcomposition prepared by combining: a copolymer that is a polyol,polyamine, polyimine, poly(carboxylic acid), or polyanhydride thatcomprises a polysiloxane, PFPE, PEO, PIB, or PB moiety; di-, tri-, orpoly-isocyanate; and, optionally a polyol, polyamine, polyimine,poly(carboxylic acid), and/or polyanhydride that does not comprise apolysiloxane, PFPE, PEO, PIB, nor PB moiety; wherein the coatingcomposition comprises about 0.1 wt % to about 40 wt % siloxane,fluorine, PEO, PIB, or PB. In some embodiments of this aspect, thepolyol that comprises a polysiloxane, PFPE, PEO, FIB, or PB moiety isPolyol-g-PIB. In certain embodiments of this aspect, the polyanhydridethat comprises a polysiloxane, PFPE, PEO, FIB, or PB moiety isP(S-alt-MA)-g-PEO.

Another aspect of the invention provides an epoxy-based coatingcomposition prepared by combining a polymer comprising at least onefunctional moiety and at least one of a polysiloxane, PFPE, PEO, PIB,and PB moiety; an epoxy resin; and optionally a hardener; and optionallya solvent.

In certain embodiments of this aspect, the epoxy resin comprisespolyglycidyl bisphenol A diglycidyl ether, bisphenol F, bisphenol S,novolac epoxy resin, aliphatic epoxy resin, glycidylamine epoxy resin,or any combination thereof. In certain embodiments of this aspect, thepolymer comprises;

Another aspect of the invention provides a polyurethane-based coatingcomposition prepared by combining: a copolymer that is a polyol,polyamine, polyimine, poly(carboxylic acid), or polyanhydride thatcomprises a polysiloxane, PFPE, PEO, PIB, or PB moiety, or a polymerhaving a Tg of 25° C. or less as described above.

In yet another aspect, the invention provides a composition thatcomprises a major component that is a polymer having a Tg of 120° C. orhigher or is an engineering plastic; and a minor component that is apolymer having a Tg of 25° C. or less as described above and having afirst end that is capable of binding to the major component and having asecond end that remains unbound; wherein the composition is adapted tobe applied to a substrate and dried and/or cured to form a coating onthe substrate, such that the second end of at least a portion of theminor component is located at a surface of the coating; and the coatingis amphiphobic.

In another aspect the invention provides a method comprising applyingthe composition of any of the above aspects to a substrate; wherein thecomposition forms a coating on the substrate; wherein the coating isamphiphobic. Embodiment of this aspect, further include drying and/orcuring the composition to form the coating.

In an aspect, the invention provides a polyurethane-based coatingcomposition that comprises perfluoropolyether (PFPE) or polysiloxane,wherein coatings prepared from the coating composition are amphiphobic,clear, and wear-resistant. In certain embodiments of this aspect,coatings of the polyurethane-based coating composition repel water andhydrophobic liquid (e.g., hexadecane). In certain embodiments, whendroplets of water or hydrophobic liquid are placed on a substrate coatedwith a crosslinked coating prepared from the coating composition, andthe substrate is tilted, the droplets slide off. Embodiments of thisaspect are coating compositions that are from 0.1 to 40 wt % siloxaneand/or from 0.1 to 40 wt % fluorine. Embodiments of this aspect, furthercomprise embedded particles and/or a biocide. Such embedded particlesare silica, titanium dioxide, diatomaceous earth, alumina, TiO₂, and/orpigments.

In another aspect of this invention, a polyurethane-based coatingcomposition is prepared by combining: a copolymer that is a polyol thatcomprises a polysiloxane moiety and/or a polyamine that comprises asiloxane moiety, di-, tri- or poly-isocyanate, and, optionally, a polyoland/or a polyamine that does not comprise a siloxane moiety, or acopolymer that is a polyol that comprises a PFPE moiety and/or apolyamine that comprises a PFPE moiety, di-, tri- or poly-isocyanate,and, optionally, a polyol and/or a polyamine that does not comprise aPFPE moiety, wherein the polyurethane-based coating composition has from0.1 to 40 wt % siloxane and/or from 0.1 to 40 wt % fluorine. In certainembodiments of this aspect, the copolymer is a graft copolymer offormula (1):

where FS is a moiety comprising PFPE, polysiloxane, or both PFPE andpolysiloxane; R is independently a moiety that comprises a hydroxyl,amino, carboxyl, glycidyl, isocyanato, or anhydride functional groupthat is protected or unprotected; Mi are independently monomers selectedfrom styrene, acrylate, methacrylate, vinyl esters, acrylic acids,methacrylic acids; x is percentage of FS moieties and is a number from0.1% to 40%; y is percentage of R moieties and is a number from 1% to90%; n is number of repeat units. In some embodiments of this aspect, FSfurther comprises at least one moiety that links FS to the copolymer.For example FS may be linked to R or Mi of the copolymer. In someembodiments, the moiety that links FS is a methylene. In certainembodiments, FS is a monomer that has PFPE or polysiloxane as a pendantgroup. In certain embodiments of the graft copolymer, FS comprisesDemnum, Fluorolink Diol, Krytox®, Fomblin Z, or Aflunox. In certainembodiments, the coating composition comprisesP(S-MMA-MAA-BMA-IBMA-VE-EGEMA-HEMA)-g-PFPE. In some embodiments, thecomposition has 13.6%, 16.5%, 23%, 27%, or 35% fluoro density. Incertain embodiments, the coating composition comprisesP(TFEMA-co-HEMA)-g-PFPE. In some embodiments of this aspect, thecomposition has 10%, 16%, 24%, or 32% fluoro density. In certainembodiments, the coating composition comprisesP(S-MMA-MAA-BMA-IBMA-VE-EGEMA-HEMA)-g-PDMS.

In certain embodiments of the polyurethane-based coating composition ofthe above aspects, the copolymer is a block copolymer of formula (2):

where FS is a moiety comprising PFPE, polysiloxane, or both PFPE andpolysiloxane; R is independently a moiety that comprises a hydroxyl,amino, carboxyl, glycidyl, isocyanato, or anhydride functional groupthat is protected or unprotected; Mi are independently monomers selectedfrom styrene, acrylate, methacrylate, vinyl esters, acrylic acids, ormethacrylic acids; y is percentage of R moieties and is a number from 1%to 90%; n is number of repeat units.

In some embodiments of this aspect, the polyurethane-based coatingcomposition, the FS moiety is polysiloxane-b-polyacrylate,polysiloxane-b-polymethacrylate, polysiloxane-b-polyacrylic acid,polysiloxane-b-polymethacrylic acid, polysiloxane-b-polystyrene,polysiloxane-b-polyvinyl ester, PFPE-b-polyacrylate,PFPE-b-polymethacrylate, PFPE-b-polyacrylic acid, PFPE-b-polymethacrylicacid, PFPE-b-polystyrene, or PFPE-b-poly(vinyl ester).

In certain embodiments of the block copolymer, the PFPE moiety isDemnum, Fluorolink®, Krytox®, or Aflunox. In some embodiments, thecoating composition comprises PFPE-b-P(HEMA-S-MMA), orPDMS-b-[HEMA-S-MMA]. In certain embodiments, the copolymer'spolysiloxane moiety is a PDMS. In certain embodiments, the polysiloxanehas a glass transition temperature in the range of −60° C. to −160° C.In certain embodiments, the polysiloxane has a glass transitiontemperature in the range of −40° C. to −160° C. In some embodiments, thepolysiloxane has a glass transition temperature in the range from −100°C. to −130° C. In certain embodiments, the PFPE moiety is a perfluoropolyether that has a glass transition temperature in the range from−150° C. to −10° C. In certain embodiments, the PFPE moiety is aperfluoro polyether that has a glass transition temperature in the rangefrom −160° C. to −10° C. In certain embodiments, the glass transitiontemperature is in the range from −130° C. to −50° C. In someembodiments, the coating composition has a wt % siloxane from 0.1% to40%. In certain embodiments, the coating composition has a wt % fluorinefrom 0.1% to 40%. In certain embodiments, the PFPE moiety is a C₁₀ toC₂₀₀₀ perfluoro polyether moiety. In some embodiments, monomers of FSinclude CH₂═C(CH₃)COOCH₂CH₂OOCCF(CF₃)[CF₂—CF(CF₃)O]_(i)CF₃. In someembodiments, monomers of FS comprise CH₂═CH—CO₂-PFPE, CH₂═CH—CO₂-Krytox,CH₂═C(CH₃)—CO₂-PFPE, CH₂═C(CH₃)—CO₂-Krytox, orCH₂═C(CH₃)COOCH₂CH₂OOCCF(CF₃)[CF₂—CF(CF₃)O]_(i)CF₃. In certainembodiments, the FS moiety is polysiloxane-g-polyacrylate,polysiloxane-g-polymethacrylate, polysiloxane-g-polyacrylic acid,polysiloxane-g-polymethacrylic acid, polysiloxane-g-polystyrene,polysiloxane-g-polyvinyl ester, PFPE-g-polyacrylate,PFPE-g-polymethacrylate, PFPE-g-polyacrylic acid, PFPE-g-polymethacrylicacid, PFPE-g-polystyrene, or PFPE-g-polyvinyl ester. In certainembodiments, the FS moiety is polysiloxane grafted to a polymer, whereinthe polymer is selected from polyacrylate, polymethacrylate, polyacrylicacid, polymethacrylic acid, polystyrene, polyvinyl ester, or a randomcopolymer that comprises acrylates, methacrylates, styrenes, and vinylesters. Another aspect of the invention providespoly(acrylate-styrene-methacrylate-vinyl ether)-g-polysiloxane. Yetanother aspect of the invention providespoly(acrylate-styrene-methacrylate-vinyl ether)-g-PFPE.

In some embodiments of the above aspects regarding compounds of formula(1) and (2), protected R groups can be deprotected by heating, exposingto moisture, or exposing to irradiation.

In another aspect, the invention provides a method of making apolyurethane-based coating composition comprising combining a copolymerthat is a polyol that comprises a siloxane moiety and/or a polyaminethat comprises a siloxane moiety, di-, tri- or poly-isocyanate, and,optionally, after allowing reaction to proceed, a polyol and/or apolyamine that do not comprise a siloxane moiety. In some embodiments ofthis aspect, the copolymer is a compound of formula (1).

In yet another aspect, the invention provides a method of making apolyurethane-based coating composition comprising combining a copolymerthat is a polyol that comprises a fluorinated moiety and/or a polyaminethat comprises a PFPE moiety, di-, tri- or poly-isocyanate, and,optionally, a polyol and/or a polyamine that do not comprise a PFPEmoiety. In an embodiment of this aspect, the copolymer is a compound offormula (2). In certain embodiments, the polyurethane-based coatingcomposition has from 1 to 40 wt % siloxane. In some embodiments, thepolyurethane-based coating composition has from 1 to 40 wt % fluorine.

In an aspect, the invention provides a method of using a clear,amphiphobic coating comprising the coating composition of the aboveaspects.

In another aspect, the invention provides a method of making a clear,amphiphobic coating on a substrate, comprising combining the followingto form a mixture (i) a copolymer that is a polyol that comprises apolysiloxane moiety, (ii) di-, tri- or poly-isocyanate, and, (iii) afirst solvent that solvates the mixture; heating, optionally, adding(iv) a polyol that does not comprise a polysiloxane moiety, andcontinuing to apply heat, cooling, adding a second solvent thatselectively solvates a portion of the mixture, the solvated portionbeing that which is not the polysiloxane moiety, removing the firstsolvent under reduced pressure, adding additional second solvent to forma coating solution, dispensing the coating solution onto a surface of asubstrate, drying the coated substrate, curing the coating. In someembodiments of the above aspect, the first solvent is acetone and/or thesecond solvent is acetonitrile. In some embodiments of this aspect,curing is heating, adding a curing catalyst (e.g., a tertiary amine,Dibutyltin dilaurate), or both heating and adding a curing catalyst.

In an aspect, the invention provides a method of forming a clearamphiphobic coating on a substrate, comprising combining the followingto form a mixture (i) a copolymer that is a polyol that comprises a PFPEmoiety, (ii) di-, tri- or poly-isocyanate, and, optionally, adding (iii)a polyol that does not comprise a PFPE moiety, and adding a solvent thatsolvates a portion of the mixture, the solvated portion being that whichis not the PFPE moiety to form a coating solution, applying the coatingsolution onto a surface of a substrate, drying the coated substrate, andcuring the coating. In some embodiments of this aspect, the solvent istetrahydrofuran. In some embodiments of this aspect, the coatingsolution is disposed on an applicator. In certain embodiments, thecoating solution is applied in a volume of solution sufficient to form afilm thickness of 0.1 to 100 microns. In some embodiments of thisaspect, the dispensing the coating solution is pipetting a volume ofsolution sufficient to form a film thickness of 2 to 15 microns. In someembodiments of this aspect, the dispensing the coating solution ispipetting a volume of solution sufficient to form a film thickness of 5to 10 microns. In some embodiments, the applying the coating solutioncomprises brushing, rolling, dip-coating, solution casting,aero-spraying, and dispensing the coating solution. In an embodiment ofthis aspect, a substrate is metal, metal oxide, ceramic, concrete,glass, masonry, stone, wood, wood composite, wood laminate, cardboard,paper, printing paper, semiconductor, plastic, rubber, leather, suede,fabric, fiber or textile. A fabric, fiber or textile may comprise, e.g.,cotton, wool, polyester, linen, ramie, acetate, rayon, nylon, silk,jute, velvet, army fabric or vinyl. In an embodiment, a fabric, fiber ortextile comprises natural fibers, synthetic fibers, or a mixturethereof.

In another aspect, the invention provides a polyol comprisingperfluoropolyether (PFPE).

In yet another aspect, the invention provides a polyol comprisingpolysiloxane.

In embodiments of these polyol aspects, the polyol is a graft copolymerof formula (1) or a block copolymer of formula (2) as described above.In certain embodiments, FS further comprise at least one moiety thatlinks FS to R or Mi of the copolymer. In some embodiments, the moietythat links FS is a methylene. In some embodiments, FS is a monomer thathas PFPE or polysiloxane as a pendant group. In some embodiments, thepolyol has 13.6%, 16.5%, 23%, 27%, or 35% fluoro density. In someembodiments, monomers of FS include CH₂═CH—CO₂-polysiloxane,CH₂═CH—CO₂-PDMS, CH₂═C(CH₃)—CO₂-polysiloxane, or CH₂═C(CH₃)—CO₂-PDMS. Incertain embodiments, the PFPE moiety is Demnum, Fluorolink Diol, FomblinZ, Krytox®, or Aflunox. In some embodiments, the polyol's polysiloxanemoiety is a PDMS. In some embodiments, the polyol's polysiloxane moietyhas a glass transition temperature in the range of −160° C. to −60° C.or the range of −130° C. to −100° C. In some embodiments, the polyol'sPFPE moiety is a perfluoro polyether that has a glass transitiontemperature in the range from −160° C. to −10° C. or in the range from−130° C. to −50° C.

In further embodiments of these polyol aspects, monomers of FS includeCH₂═CH—CO₂-PFPE, CH₂═CH—CO₂-Krytox, CH₂═C(CH₃)—CO₂-PFPE,CH₂═C(CH₃)—CO₂-Krytox, orCH₂═C(CH₃)COOCH₂CH₂OOCCF(CF₃)[CF₂—CF(CF₃)O]_(i)CF₃. In some embodiments,the FS moiety is polysiloxane grafted to a polymer, wherein the polymeris selected from polyacrylate, polymethacrylate, polyacrylic acid,polymethacrylic acid, polystyrene, polyvinyl ester, or a randomcopolymer that comprises acrylates, methacrylates, styrenes, and vinylesters. In some embodiments, the FS moiety is PFPE grafted to a polymer,wherein the polymer is selected from polyacrylate, polymethacrylate,polyacrylic acid, polymethacrylic acid, polystyrene, polyvinyl ester, ora random copolymer that comprises acrylates, methacrylates, styrenes,and/or vinyl esters. In some embodiments, the polyol ispolysiloxane-g-poly(acrylate-styrene-methacrylate-vinyl ester),polysiloxane-g-poly(styrene-methacrylate-vinyl ester),polysiloxane-g-poly(acrylate-methacrylate-vinyl ester),polysiloxane-g-poly(acrylate-styrene-vinyl ester),polysiloxane-g-poly(acrylate-styrene-methacrylate),PFPE-g-poly(acrylate-styrene-methacrylate-vinyl ester),PFPE-g-poly(styrene-methacrylate-vinyl ester),PFPE-g-poly(acrylate-methacrylate-vinyl ester),PFPE-g-poly(acrylate-styrene-vinyl ester),PFPE-g-poly(acrylate-styrene-methacrylate), PFPE-g-P(HEMA-S-MMA), orPDMS-g-[HEMA-S-MMA].

In some polyol embodiments, FS further comprises at least one moietythat links FS to R or Mi. In some embodiments, the moiety that links FSis a methylene. In some embodiments, FS is a monomer that has PFPE orpolysiloxane as a pendant group. In certain embodiments, the FS moietyis Demnum, Fluorlink Diol, Fomblin Z, Krytox®, or Aflunox. In someembodiments, the copolymer's polysiloxane moiety is a PDMS. In someembodiments, the polyol is PFPE-b-poly(acrylate-hydroxy (meth)acrylate,PFPE-b-poly(methacrylate-hydroxy (meth)acrylate),PFPE-b-poly(styrene-hydroxy (meth)acrylate), or PFPE-b-poly(vinylester-hydroxy (meth)acrylate). In some embodiments, the polyol ispolysiloxane-b-poly(methacrylate-hydroxy(meth)acrylate),polysiloxane-b-poly(acrylic acid-hydroxy(meth)acrylate),polysiloxane-b-poly(styrene-hydroxy(meth)acrylate),polysiloxane-b-poly(vinyl ester-hydroxy(meth)acrylate),PFPE-b-poly(acrylate-hydroxy(meth)acrylate,PFPE-b-poly(methacrylate-hydroxy(meth)acrylate),PFPE-b-poly(styrene-hydroxy(meth)acrylate), or PFPE-b-poly(vinylester-hydroxy (meth)acrylate). In further embodiments, the polyolcomprises hydroxy styrenes or vinyl alcohols.

In yet another aspect, the invention provides a method of making a clearamphiphobic coating on a substrate, which includes combining thefollowing solutions to form a mixture: a solution of a copolymer that isa polyol that comprises a polysiloxane moiety, in a minimum amount of afirst solvent; a solution of di-, tri- or poly-isocyanate bearingprotecting groups on its isocyanate moieties, in a minimum amount of afirst solvent, and, optionally, a solution of a polyol that does notcomprise a polysiloxane moiety, in a minimum amount of a first solvent,wherein the first solvent is not water but is substantiallywater-miscible, adding water to the mixture; reducing the volume so thatthe first solvent is substantially removed thereby forming an aqueouscoating solution; dispensing the aqueous coating solution onto a surfaceof a substrate; drying the coated substrate; and curing the coating. Insome embodiments of this aspect, the first solvent is a ketone (e.g.,acetone, ethylmethylketone), THE, ester (e.g., ethyl acetate), or1,2-dimethoxyethane.

In another aspect, the invention provides a method of making a clearamphiphobic coating on a substrate, comprising combining the followingto form a mixture: (i) a copolymer that is a polyol that comprises apolysiloxane moiety; (ii) di-, tri- or poly-isocyanate; and (iii) asolvent that solvates the mixture, heating, optionally, adding (iv) apolyol that does not comprise a polysiloxane moiety, and continuing toapply heat, cooling, dispensing the coating solution onto a surface of asubstrate, drying the coated substrate, and curing the coating. In someembodiments of this aspect, the solvent is ketone (e.g., acetone,ethylmethylketone), ester (e.g., ethyl acetate), or 1,2-dimethoxyethane.

In another aspect, the invention provides a method of making a clearamphiphobic coating on a substrate, comprising combining the followingto form a mixture: (i) a copolymer that is a polyol that comprises apolysiloxane moiety; (ii) di-, tri- or poly-isocyanate; and, (iii) afirst solvent that solvates the mixture, optionally, adding (iv) apolyol that does not comprise a polysiloxane moiety, adding a secondsolvent that selectively solvates a portion of the mixture, the solvatedportion being that which is not the polysiloxane moiety, removing thefirst solvent under reduced pressure, adding additional second solventto form a coating solution, dispensing the coating solution onto asurface of a substrate, drying the coated substrate, and curing thecoating. In some embodiments of this aspect, the first solvent is ketone(e.g., acetone, ethylmethylketone), THF, esters (e.g., ethyl acetate),or 1,2-dimethoxyethane. In certain embodiments of this aspect, thesecond solvent is the second solvent is acetonitrile or dimethylcarbonate.

In one aspect, the invention provides an epoxy-based coating compositionthat comprises polysiloxane and/or fluorinated moieties, whereincrosslinked coatings prepared from the coating composition areamphiphobic, anti-smudge, clear and wear-resistant.

In embodiments of the above aspect, when droplets of water orhydrophobic liquid are placed on a substrate coated with a crosslinkedcoating prepared from the coating composition, and the substrate istilted, the droplets slide off. In embodiments of the above aspect, theepoxy-based coating composition is from 0.1 to 40% wt % siloxane and/orfrom 0.1 to 40% wt % fluorine. In embodiments of the above aspect, thecoating composition further includes embedded particles and/or abiocide. In embodiments of the above aspect, the embedded particles aresilica, titania, diatomaceous earth, alumina, TiO₂, and/or pigments.

In another aspect, the invention provides a coating composition preparedby combining a polymer comprising functional moieties, and polysiloxanemoieties or fluorinated moieties, an epoxy resin, a hardener, andoptionally a solvent. In embodiments of the above aspect, the hardenercomprises a polyamine, a polyol, a polyimine, a poly(anhydride), apoly(carboxylic acid), a polyphenol, a polythiol, or any combinationthereof, wherein poly is 2 or more than 2. In embodiments of the aboveaspect, the polyanhydride is an oligomer of styrene and maleicanhydride.

In embodiments of the above aspect, the hardener comprisespoly(oxypropylene) diamine, nonylphenol, triethanolamine and piperazine.In embodiments of the above aspect, the polyol is triethanolamine, anoligomer containing hydroxyl-bearing monomer units such as2-hydroxylethyl methacrylate or 2-hydroxyethyl acrylate, glycerol,ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, propylene glycol, dipropylene glycol, tripropylene glycol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol,1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanolamine, diethanolamine,methyldiethanolamine, phenyldiethanolamine, glycerol,trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, pentaerythritol,or N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine.

In other embodiments of the above aspect, the polyamine ispoly(oxypropylene) diamine, poly(ethylene imine), ethylenediamine (EDA),diethylenetriamine (DETA), dipropylene triamine (DPTA),methylenetetramine (TETA), tetraethylene pentamine (TEPA), diethylaminopropylamine (DEAPA), 3-dimethylaminopropylamine (DMAPA),trimethylhexamethylenediamine (TMDA), isophoronediamine (IPDA),N-aminoethyl piperazine, 3,3′-dimethyl-4,4-diaminodi-cyclohexylmethane,4,4′-diaminodiphenylmethane (DDM), m-Phenylene diamine (MPDA),p,p′-diaminodiphenylsulphone (DDs), 2,4,6-tris-dimethylaminomethyiphenol(tris-DMP), or 1,3-xylylene diamine. In certain embodiments of the aboveaspect, the poly(anhydride) is an oligomer of styrene and maleicanhydride, phthalic anhydride (PA), maleic anhydride (MA),methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalicanhydride (MTWPA), hexahydrophthalic anhydride (HHPA), trimelliticanhydride (TMA), or dodecenyl-succinic anhydride (DSA).

In embodiments of the above aspect, the epoxy resin comprisespolyglycidyl bisphenol A diglycidyl ether, bisphenol F, bisphenol S,novolac epoxy resin, aliphatic epoxy resin, glycidylamine epoxy resin,and/or a combination thereof. In embodiments of the above aspect, thepolysiloxane moieties comprise PDMS. In embodiments of the above aspect,fluorinated moieties comprise perfluorinated polyether or PFPE (e.g.,PFPO, Demnum, Fluorolink).

In embodiments of the above aspect, the coating has a weight percentageof PDMS in a range of 0.1 wt % to 40 wt %. In embodiments of the aboveaspect, the coating has a weight percentage of PDMS in a range of 1.0and 10 wt %. In embodiments of the above aspect, the coating has aweight percentage of PDMS of 1.0%, 5.0%, 8.0% or 12%. In embodiments ofthe above aspect, the coating has a weight percentage of PFPE in a rangeof 0.1 wt % to 40 wt %. In embodiments of the above aspect, the coatinghas a weight percentage of PFPE (e.g., PFPO) of 1.0%, 5.0%, 8.0% and12%.

In an aspect, the invention provides use of a clear amphiphobic coatingcomprising the coating of any one of the aspects described above orembodiments thereof.

In yet another aspect, the invention provides a method of making acoating composition comprising combining a polymer, which comprisesfunctional moieties and siloxane moieties or fluorinated moieties, withan epoxy resin, optionally a solvent, and a hardener.

In embodiments of the above aspect, the optional solvent isacetonitrile, dimethylformamide, tetrahydrofuran, ketone (e.g., acetone,ethylmethylketone), esters (e.g., ethyl acetate), 1,2-dimethoxyethane,acetonitrile, chloroform, or pyridine.

In an aspect, the invention provides use of an amphiphobic epoxy-basedcomposition comprising the composition of any one of the above aspectsand embodiments thereof.

In another aspect, the invention provides a method of forming a clearamphiphobic coating on a substrate, comprising combining the followingto form a mixture: a polymer comprising functional moieties, andpolysiloxane moieties or fluorinated moieties, and an epoxy resin,optionally a solvent, and a hardener; applying the coating solution ontoa surface of a substrate; drying the coated substrate; and curing thecoating.

In embodiments of the above aspect, the applying the coating solution isapplying a volume of solution sufficient to form a film thickness ofabout 1 μm to about 1 mm.

In embodiments of the above aspect, the applying the coating solutioncomprises brushing, rolling, dip-coating, solution casting,aero-spraying, and dispensing the coating solution. In embodiments ofthe above aspect, the functional moieties comprise amine, imine,hydroxyl, carboxyl, and/or anhydride.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the invention and to show more clearly howit may be carried into effect, reference will now be made by way ofexample to the accompanying drawings, which illustrate aspects andfeatures according to embodiments of the present invention, and inwhich:

FIG. 1 shows a graph of sliding angle vs. F wt % fluorine content forfilms prepared from polymer of Example 1A(i).

FIG. 2 shows a graph of % T vs. fluorine content for films prepared fromExample 1A(i) where the % T values were recorded at a wavelength of 500nm.

FIG. 3 graphically shows variation in the sliding angles vs. NCO/OHratio for Example 1A(i) based FPU films. Solid lines show sliding anglesmeasured before a rubbing test, while dotted lines denote sliding anglesmeasured after a rubbing test. Rubbing tests were performed using a 400g weight for 40 min at 40 rpm. The sliding angle tests were performedusing 20 μL water droplets and 5 μL hexadecane droplets.

FIG. 4 shows photographs of artificial fingerprint impressions that wereapplied onto (a) ordinary glass; (b) glass coated with coating ofExample 1A(i); (c) glass coated with coating of Example 1A(ii); and (d)glass coated with coating of Example 1C(ii).

FIG. 5 shows % Transmittance spectra over a range of 450-750 nm observedfor (a) uncoated glass; (b) unmodified drop cast polyurethane films; (c)PFPE PU films prepared from Example 1B(i); (d) PFPE PU films preparedfrom Example 1A(i); (e) PFPE PU films prepared from Example 1A(ii); (f)spin coated PFPE PU film just a few nm in thickness prepared fromExample 1A(i); and (g) spin coated PFPE PU film just a few nm inthickness prepared from Example 1A(ii). All spin coated samplesexhibited high % T values.

FIG. 6 shows an anti-ink test performed at the junction of uncoatedglass and coated glass. Various coated samples that had been marked witha permanent marker (top row) and were subsequently cleaned via wiping(bottom row). Coatings were as follows:

a) unmodified PU bearing marker line;

b) PFPE PU films prepared from Example 1A(i) bearing marker line oncoated glass to the left of the arrow, and bearing marker line onuncoated glass to the right of the arrow (notably, on the coated glassthe marker ink is unable to form a line but instead appears as smallround balls of ink);

c) PFPE PU films prepared from Example 1B(ii) bearing marker line oncoated glass to the left of the arrow, and bearing marker line onuncoated glass to the right of the arrow (notably, on the coated glassthe marker ink is unable to form a line but instead appears as smallround balls of ink);

d) PDMS PU film from Example 1C(i) bearing marker line on coated glassto the right and uncoated glass to the left ((notably, on the coatedglass the marker ink is unable to form a line but instead appears assmall round balls of ink).

a1) unmodified PU after wiping;

b1) Example 1A(i) PFPE PU after wiping which shows that the ink that wason the coated glass (left of arrow) has wiped away completely, while theink on the uncoated glass (right of arrow) remains;

c1) Example 1B(i) PFPE PU after wiping which shows that the ink that wason the coated glass (left of arrow) has wiped away completely, while theink on the uncoated glass (right of arrow) remains.

d1) PDMS PU film from Example 1C(i) after wiping which shows that theink that was on the coated glass (right) has wiped away completely,while the ink on the uncoated glass (left) remains.

FIG. 7 shows a schematic representing PFPE or PDMS modified PU films.

FIG. 8 shows sliding angles for water and hexadecane with varying PDMScontent of PDMS PU prepared from Example 1C(i).

FIG. 9 shows time-sequence pictures of hexadecane on FPU-coated steeland wooden surfaces. In addition, images of a water droplet testperformed on a FPU-coated cotton sample are also shown.

FIG. 10 shows a schematic overview of the preparation of epoxy-basedamphiphobic clear coatings.

FIG. 11 shows structural formulae for P20-1 and P20-2, which differ inregard to n.

FIG. 12 shows structural formulae for P20-3.

FIG. 13 shows structural formulae for P20-4.

FIG. 14 shows structural formulae for P20-5.

FIG. 15 shows structural formulae for P20-6.

FIG. 16 shows structural formulae for P20-7.

FIG. 17 shows structural formulae for P20-8.

FIG. 18 graphically shows the relationship between transmittance andcoating thickness for PEI-g-PDMS epoxy films, which were made with amixture of other hardeners including polyoxypropylenediamine,nonylphenol, triethanolamine and piperazine.

FIG. 19 graphically shows the relationship between contact angle andPDMS wt %.

FIG. 20 graphically shows the relationship between sliding angle andPDMS wt %.

FIG. 21A unreacted PDMS (%) as determined by integration of the PDMSpeak from

FIG. 21B was plotted versus reaction time.

FIG. 21B graphically shows GPC traces at different time points, with PS(polystyrene) as a standard reference peak. As shown at the right handside, the amount of unreacted PDMS diminishes as the reactionprogresses.

FIG. 22A displays ATR-IR (attenuated total reflectance infrared (ALPHAinstrument available through Bruker) spectra recorded during the thermalcuring of a PDMS modified epoxy resin film (specifically Bis-A) at 150°C. under the conditions of Example 39A where PEI-g-PDMS was the onlyhardener present.

FIG. 22B displays ATR-IR (attenuated total reflectance infrared (ALPHAinstrument available through Bruker) spectra recorded during the thermalcuring of a PDMS modified epoxy resin film (specifically EDGBA or Bis-A)at 120° C. under the conditions of Example 40 where PEI-g-PDMS is mixedwith a mixture of other hardeners including polyoxypropylenediamine,nonylphenol, triethanolamine and piperazine.

FIG. 23 is a plot of Transmittance versus film thickness at 500 nm forPEI-g-PDMS modified epoxy coatings as a functions of film thickness atPDMS wt % of 2.1%, 4.0%, 7.4%, and 10.3%, for films made with no otherhardeners than the PEI-g-PDMS.

FIG. 24a-h shows anti-graffiti properties of PEI-g-PDMS modified epoxycoatings having 4.0 wt % PDMS as well as unmodified “regular” epoxycoatings. FIG. 24a shows the unmodified coating on avertically-positioned glass slide after oil based spray Paint A has beensprayed on it. FIG. 24b shows modified coating on avertically-positioned glass slide after Paint A has been sprayed on it;notice how the paint has slid off to the bottom. FIG. 24c shows theunmodified coating on a vertically-positioned glass slide after oilbased spray Paint B had been sprayed on it. FIG. 24d shows modifiedcoating on a vertically-positioned glass slide after Paint B had beensprayed on it; notice how the paint has slid off to the bottom. FIG. 24eshows a glass slide bearing unmodified coating after a permanent blackmarker has been used to draw a black mark on it. FIG. 24f shows a glassslide bearing modified coating after a permanent black marker has beenused to draw a black mark on it, note that the ink does not stick andhas formed little balls of ink on the surface. FIG. 24g shows the sameslide as 24 f when a portion of the marker mark has been wiped with adry tissue. FIG. 24h shows a glass slide bearing modified coating aftera rubbing test was conducted for 18 hours, following the rubbing, ablack marker has been used to draw a black mark on it, note that thecoating has exhibit good durability and the ink does not stick.

FIG. 25 shows a schematic that illustrates a matrix and surfacepolymers.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

As used herein, the term “unsubstituted” refers to any open valence ofan atom being occupied by hydrogen. Also, if an occupant of an openvalence position on an atom is not specified then it is hydrogen.

As used herein, a “functional group” is a specific atom or group ofatoms within a molecule that are responsible for characteristic chemicalreactions. Thus functional groups are moieties within a molecule thatare likely to participate in chemical reactions.

As used herein, “aliphatic” refers to hydrocarbon moieties that arestraight chain, branched or cyclic, may be alkyl, alkenyl or alkynyl,and may be substituted or unsubstituted. “Short chain aliphatic” or“lower aliphatic” refers to C₁ to C₄ aliphatic. “Long chain aliphatic”or “higher aliphatic” refers to C₅ to C₂₅ aliphatic.

As used herein, an “amphiphobic” material or surface is one that is bothhydrophobic and oleophobic or lipophobic. In an embodiment, a materialor surface is considered to be amphiphobic when drops of oil (i.e.,hydrophobic liquid) and drops of water roll readily off the material orsurface when the material or surface is tilted from the horizontalposition at an angle of 90 degrees or less. It should be understood thatthe term “amphiphobic” is not limited to repelling only water and oil.In certain embodiments, an amphiphobic material or surface will repelnot only water and oil but also other substances, such as fingerprints,salt, acid, base, bacteria, etc.

As used herein, “heteroatom” refers to non-hydrogen and non-carbonatoms, such as, for example, O, S, P, and N.

As used herein, “polymer” refers to a large molecule, or macromolecule,composed of many repeated units.

As used herein, the term “copolymer” refers to a polymer having morethan one type of monomer units. As used herein, the term “co” refers tocopolymer.

As used herein, the term “grafted copolymer” refers to a copolymer witha linear backbone of one polymer and randomly distributed side chains ofanother polymer.

As used herein, the term “b” refers to block.

As used herein the term “block copolymer” refers to a type of copolymerthat is made up of blocks of different polymerized monomers. Blockcopolymers may be prepared by first polymerizing a first polymer from afirst monomer, and then subsequently polymerizing a second monomer fromthe reactive end of the first polymer. The resultant polymer is a“diblock copolymer” because it contains two different chemical blocks.Triblocks, tetrablocks, multiblocks, etc. can also be made.

As used herein, the term “engineering plastic” refers to plasticmaterials that have better mechanical and/or thermal properties than themore widely used commodity plastics.

As used herein, the term “PU”, or “polyurethane” refers to a polymercomposed of a chain or a network of subunits joined by carbamate(urethane) links. Polyurethane polymers are most commonly formed byreacting an isocyanate with a polyol.

As used herein, the term “FPU” refers to a modified polyurethane thatincludes perfluoropolyether moieties.

As used herein, the term “PDMSPU” refers to a polyurethane that ismodified and includes polydimethylsiloxane moieties.

As used herein, the term “HDID” refers to hexamethylene diisocyanatedimer.

As used herein, the term “PS” refers to polystyrene.

As used herein, the term “PDMS” refers to polydimethylsiloxane.

As used herein, the term “PDMS-epoxy” refers to an epoxy that includespolydimethylsiloxane moieties.

As used herein, the term “PFPO” refers to poly(perfluoroisopropyleneoxide).

As used herein, the term “PFPO-epoxy” refers to an epoxy that includespoly(perfluoroisopropylene oxide) moieties.

As used herein, the term “PFPE” refers to perfluoropolyether, examplesof PFPEs include PFPO, Demnum (available from Daikin), or Fluorolink(available from Solvay.

As used herein, the term “P1” refers to a solid powder that is P(S-MMA-MAA-BMA-iPMA-VP-HEGEMA-HEMA) having the full name asPoly(styrene-methyl methacrylate-methacrylic acid-butylmethacrylate-isopentyl methacrylate-vinyl propanoate-(2-hydroxy-ethyleneglycol)ethyl methacrylate-2-hydroxyethyl methacrylate). P1 is a powderedsolid that is obtained by adding P1-0 to a hexane and ether mixture.

As used herein, the term “P1-0” refers to a commercially-availablesolution of unmodified polyol P1.

As used herein, the terms “P10” “P20” and “P30” refer to polymers whosestructural formulae are shown in FIGS. 10-17.

As used herein, the term “PB” refers to polybutadiene.

As used herein, the term “PIB” refers to polyisobutylene.

As used herein, the term “PEI” refers to polyethylenimine.

As used herein, the term “PEO” refers to poly (ethylene glycol) methylether.

As used herein, the term “S” refers to styrene.

As used herein, the term “DMF” refers to N,N-dimethylformamide.

As used herein, the term “GPC” refers to gel permeation chromatography.

As used herein, the term “MA” refers to maleic anhydride.

As used herein, the term “MMA” refers to methyl methacrylate.

As used herein, the term “HDID” refers to dimeric hexamethylenediisocyanate.

As used herein, the term “HEMA” refers to 2-hydroxy ethyl methacrylate.

As used herein, the term “MAA” refers to methacrylic acid.

As used herein, the term “BMA” refers to butyl methacrylate.

As used herein, the term “iPMA” refers to isopentyl methacrylate.

As used herein, the term “VP” refers to vinyl propanoate.

As used herein, the term “HEGEMA” refers to 2-(hydroxyl ethyleneglycol)ethyl methacrylate.

As used herein, the term “HEMA” refers to 2-hydroxyethyl methacrylate.

As used herein, the term “ATRP” refers to atom transfer radicalpolymerization.

As used herein, the term “PFPE-COOH” refers to perfluoropolyethercarboxylic acid.

As used herein, the term “FEGEMA” refers to PFPE grafted EGEMA.

As used herein, the term “FEMA” refers to PFPE grafted HEMA.

As used herein, the term “P[(S-MMA-MAA-BMA-IBMA-VP-EGEMA-HEMA)-g-PFPE]”refers to perfluoropolyether graftedP(S-MMA-MAA-BMA-IBMA-VE-EGEMA-HEMA).

As used herein, the term “P[(S-MMA-MAA-BMA-IBMA-VP-EGEMA-HEMA)-g-PDMS]”refers to poly(dimethyl siloxane) graftedP(S-MMA-MAA-BMA-IBMA-VE-EGEMA-HEMA).

As used herein, the term “EBrIB” refers to ethyl α-bromoisobutyrate.

As used herein, the term “P(TFEMA-co-HEMA)” refers to copolymerpoly(trifluoroethyl methacrylate-co-2-hydroxyethyl methacrylate).

As used herein, the term “P(HEMA-S-MMA)” refers to a copolymerpoly((2-hydroxyethyl methacrylate)-styrene-methyl methacrylate).

As used herein, the term “PEI-g-PDMS” refers to polyethylenimine-g-PDMS.

As used herein, the term “P(S-alt-MA)-g-PDMS” refers toPoly(styrene-alt-maleic anhydride)-g-PDMS.

As used herein, the term “TFEMA” refers to trifluoroethyl methacrylate.

As used herein, the term “PGMA” refers to poly(glycidyl methacrylate).

As used herein, the term “% T” refers to percent transmittance.

As used herein, the term “fluoro density” refers to the percentage ofhydroxyl side chains that have been replaced by fluorinated moietiessuch as PFPE. For example, 13.6% fluoro density refers to a polymerwherein 86.4% of the hydroxyl groups remain, and 13.6% of the positionsthat were formally hydroxyl are now occupied by PFPEs.

As used herein, the term “siloxane density” refers to the percentage ofhydroxyl side chains that have been replaced by siloxane such as PDMS.For example, 11.3% siloxane density refers to a polymer wherein 88.7% ofthe hydroxyl groups remain, and 11.3% of the positions that wereformally hydroxyl are now occupied by PDMS chains.

Embodiments

Embodiments of the invention provide coating compositions that arecapable of forming a coating that has oil- and water-repellentproperties. The major component of the coating is in contact with acoated substrate and forms a solid matrix that is formed, for example,by crosslinks that are formed in the curing process. Although the minorcomponent may be found dispersed throughout the coating, at least somespecies of the minor component are located at the surface. This surfacelocation of at least a portion of the minor component provides the curedcoating with special properties.

This surface layer has polymers that are only attached at one end whilethe other end is unbound (see FIG. 25 for an illustration). This minorcomponent is thus bound to the matrix at one end, but its other end isunbound. The second component includes a polymer that has a glasstransition temperature below 25° C. Due to the dynamic nature of thesepolymers with a relatively low Tg, these polymers are liquid-like intheir nature. (In some embodiments, these polymers are inherently waxybut may become liquid-like when plasticised by moisture adsorbed fromair or taken up from its environment.) Due to its fluid nature, thesepolymers are capable of migrating to the surface during the drying andcuring processes.

These singly-bound polymers located at the surface are constantly inmotion and are referred to herein as dynamic. The constant motion ofthese surface polymers provides amphiphobic, anti-smudge andanti-graffiti properties to the coatings. The dynamic component behaveslike a liquid, but this does not mean that the coating's surface is wet.Instead, it meansthat the surface polymers act in a liquid-like manner.As mentioned above, although the species of the dynamic component thatare conferring special properties are the ones at the surface, there areothers dispersed throughout the matrix. Because of their presencethroughout, when the coating is worn down, some of the dynamiccomponents that were formerly embedded in the matrix become newlyexposed to the surface. In this way, the amphiphobic anti-smudgeproperties of the coating endure even when the coating experiences wear.

Major Component

The major component that provides a solid matrix can be any engineeringplastic that has a high glass transition temperature or any polymer thathas a high glass transition temperature and that crosslinks to form asolid polymeric coating. In certain embodiments, the solid coating istransparent (i.e., clear). Polyurethane and epoxy are used herein asnon-limiting representative examples for this major component. Theinventors suggest that other polymers with a glass transitiontemperature that is higher than about 120° C. would also be suitable.Suitable major components include: engineering plastics with a glasstransition temperature (Tg) or with a melting temperature (Tm) ofgreater than about 100° C. Such polymers and engineering plasticsinclude: Polystyrene (PS), Polyvinyl chloride (PVC), Polypropylene (PP),Polyethylene (PE), Poly (acrylonitrile butadiene styrene) (ABS), Nylon6, Nylon 6-6, Polyamides (PA), Poly(butylene terephthalate) (PBT),Polycarbonates (PC), Poly(etheretherketone) (PEEK), Poly(etherketone)(PEK), Poly(ethylene terephthalate) (PET), Polyimides,Poly(oxymethylene) plastic (POM/Acetal), Poly(phenylene sulfide) (PPS),Poly(phenylene oxide) (PPO), Polysulfone (PSU),Poly(tetrafluoroethylene) (PTFE/Teflon), Ultra-high-molecular-weightpolyethylene (UHMWPE/UHMW). They also include Semi-crystalline orCrystalline Plastics with a Tm greater than about 50° C., such as: Nylon(PA66 and PA6), Poly(oxymethylene) (POM) Poly(ethylene terephthalate)(PET), Poly(butylene terephthalate) (PBT), Polytetrafluoroethylene(PTFE), isotactic polypropylene, atactic polypropylene, High-densitypolyethylene, or Low-density polyethylene. They also include polymersthat are cross-linkable such as Polyurethane, Epoxy resin, Polyacrylate, Polymethacrylate, Polystyrene, Polyimide, Polyamine,Polysulfone, Polyester, or Polycarbonate.

Dynamic Component

A variety of polymers have been used in the examples provided herein asthe minor component, which is dynamic (i.e., in motion). Without wishingto be bound by theory, the inventors suggest that suitable polymers forthe dynamic minor component have a Tg that is about 25° C. or that isless than 25° C. This Tg is significantly lower than the Tg of thematrix's major or core component. The dynamic quality of the minorcomponent's species that are located at the surface confer specialproperties on the coating that are desirable. Such special propertiesinclude anti-smudge, anti-wetting and amphiphobicity. Examples ofcomponents that have been shown to provide anti-smudge, anti-wetting,and amphiphobic properties include, for example, polysiloxane,perfluorinated polyether, polyisobutylene, and polybutadiene,poly(ethylene oxide) polymers, and polypropylene oxide. Non-limitingexamples include P(S-alt-MA)-g-PEO₇₅₀, P(S-alt-MA)-g-PEO₂₀₀₀,P(S-alt-MA)-g-PEO₅₀₀₀, and Polyol-g-PIB.

Representative example coatings are described herein for combinations ofcertain dynamic minor components with polyurethane as well as epoxy coremajor components. Accordingly, embodiments of the invention providepolyurethane-based coatings and adhesives and epoxy-based coatings andadhesives. Such coatings and adhesives are optically-clear, amphiphobic,and, importantly, are thick enough and durable enough to endure wear.Such coatings are suitable for a variety of surfaces and are repellentagainst both water- and oil-borne contaminants. On surfaces coated withthis durable and optically-clear amphiphobic coating, fingerprints andsmudges do not readily deposit. If they are deposited, they are readilyremovable due to repulsion of the coating against the contaminants.

Coatings that include components or moieties that exhibit dynamic chainmobility at room temperature are described herein. In embodiments of theinvention, dynamic component that are located at or near the surfacehave one end covalently linked to a crosslinked matrix while the otherend is not linked and may move around. This chain mobility allows thesechains to migrate to the surface. Although not wishing to be bound bytheory, the inventors suggest that such free movement of chains (i.e.,dynamic chain mobility at room temperature) prevents formation ofpermanent contacts between a foreign substance (e.g., rain, ink, paint,or greasy fingerprints) and the coating. Where the coating is on asurface that is flat and is lacking solid protrusions, a liquid foreignsubstance readily slides off the coated surface. Such water and oilrepellency properties of these amphiphobic polyurethane-based andepoxy-based formulations are quantified in the working examples providedherein.

The compositions described herein are useful as coatings, paints,adhesives and many other uses that traditional polyurethane- orepoxy-based compositions are used for. For simplicity, they are referredto simply as coatings herein.

Polysiloxane, perfluorinated polyethers, poly(ethylene oxide),polybutadiene, and polyisobutylene are used herein as representativeexamples for the dynamic minor component of such coatings. However,these examples should not be limiting. The inventors suggest that otherpolymers that have a glass transition temperature that is about 25° C.or less than 25° C. would also be suitable. Such polymers include:poly(alkene) and Poly(halogenated alkene) polymers such as, polyethylene(atactic) Tg=−20° C., polybutene Tg=−24° C., polyethylene (HDPE)Tg=−125° C., poly(cis-isoprene) Tg=−63° C., poly(trans-isoprene) Tg=−66°C., poly(1-octane) Tg=−63° C., atactic polypropylene, Tg=−13° C.,isotactic polypropylene, Tg=−8° C., syndiotactic polypropylene, Tg=−8°C., poly(vinyl propionate) Tg=10° C., poly(vinylidene chloride) Tg=−18°C., poly(vinylidene fluoride) Tg=−40° C., poly(cis-chlorobutadiene)Tg=20° C., poly(trans-chlorobutadiene) Tg=−40° C. They also includepolyacrylates such as, for example, poly(benzyl acrylate) Tg=6° C.,poly(butyl acrylate), Tg=−54° C., poly(sec-butyl acrylate) Tg=−26° C.,poly(2-cyanoethyl acrylate) Tg=4° C., poly(cyclohexyl acrylate) Tg=19°C., poly(dodecyl acrylate) Tg=−3° C., poly(ethyl acrylate) Tg=−24° C.,poly(2-ethylhexyl acrylate) Tg=−50° C., poly(isobutyl acrylate) Tg=−24°C., poly(2,2,2-trifluoroethyl acrylate) Tg=10° C., poly(2-ethoxyethylacrylate) Tg=−50° C., isotactic poly(isopropyl acrylate), Tg=−11° C.They also include polymethacrylates such as, poly(benzyl acrylate) Tg=6°C., poly(diethylaminoethyl methacrylate) Tg=20° C., poly(dodecylmethacrylate) Tg=−65° C., poly(2-ethylhexyl methacrylate) Tg=−10° C.,poly(hexadecyl methacrylate) Tg=15° C., poly(hexyl methacrylate) Tg=−5°C., poly(octadecyl methacrylate) Tg=−100° C., poly(octyl methacrylate)Tg=−20° C. They further include poly ethers and poly epoxides such as,for example, poly(propyl vinyl ether) Tg=−49° C., poly(methyl vinylether) Tg=−31° C., poly(methyl glycidyl ether) Tg=62° C., poly(isobutylvinyl ether) Tg=−19° C., poly(ethyl vinyl ether) Tg=−43° C.,poly(2-ethylhexyl vinyl ether) Tg=−66° C., poly(dodecyl vinyl ether)Tg=−62° C., poly(butyl vinyl ether) Tg=−55° C., poly(butyl glydicylether) Tg=−79° C., poly(allyl glycidyl ether) Tg=−78° C., poly(ethyleneoxide) Tg=−66° C., poly(propylene oxide) Tg=−75° C.,poly(tetrahydrofuran) Tg=−84° C., poly(1,2-epoxybutane) Tg=−70° C.,poly(1,2-epoxydecane) Tg=−70° C., poly(1,2-epoxyoctane) Tg=67° C.,poly(epibromohydrin) Tg=−14° C., poly(epichlorohydrin) Tg=−22° C.,poly(trimethylene oxide) Tg=−78° C., poly(epibromohydrin) Tg=−14° C.,poly(epichlorohydrin) Tg=−22° C. They also include poly esters such as,poly(tetramethylene terephthalate) Tg=17° C., poly(tetramethyleneadipate) Tg=−118° C., poly(ethylene malonate) Tg=−29° C., poly(ethyleneadipate) Tg=−46° C., or poly(ϵ-caprolactone) Tg=−60° C. They furtherinclude poly siloxanes such as, for example, poly(dimethylsiloxane)Tg=−127° C., or poly(methylphenylsiloxane) Tg=86° C. They also includefluoropolymers, perfluoro polymers and phosphazene polymers such as, forexample,

where R is CH₃, C₆H₅, OCH₃, OCH₅, NR₂, Cl, Br, F, OCH₂CF₃, or OCH₂C₆H₅.They also include poly ionic liquids such as, for example,Poly(1-glycidyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide).Other examples of such dynamic species include poly(formaldehyde)Tg=−82° C., poly(ethylene-trans-1,4-cyclohexyldicarboxylate) Tg=18° C.,or poly(acetaldehyde) Tg=−32° C.

Polyurethane- and epoxy-based coatings have been investigated asrepresentative examples of the major component of such coatings. Manystudies regarding methods of making and characterization of the curedcoating have been conducted and are described herein. In regard to themethod of making the coatings, several techniques have been investigatedregarding methods of making the clear amphiphobic coatings. Detailedsteps are provided herein. Briefly, techniques were developed to attachthe dynamic component to a reactant of polyurethane or to a reactant ofepoxy. Importantly, it was also possible to merely add the dynamiccomponent to the mixture of polyurethane reactants and not performinitial reactions to attach the dynamic component to one of thereactants. This technique allows the dynamic component to be soldseparately as an additive (prior to drying/curing) that providesamphiphobic properties to an engineering plastic or any polymer that hasa high glass transition temperature and that is capable of forming asolid polymeric coating. Details are provided in the Working Examples.

Polyurethane-Based Coatings

An optically-clear, amphiphobic, and durable polyurethane-based coatingcomposition has been prepared and its properties have been quantified.This composition is prepared by including a new component to thetraditional PU formulation of isocyanate and polyol. The new componentis a polyol that bears PFPE, polysiloxane, or both PFPE andpolysiloxane. This component may be an additive to the traditionalformulation or it is may be used as a replacement in the absence of“regular” or “unmodified” polyol (that is, a polyol that does notcomprise PFPE or polysiloxane). Specifically, this new coatingcomposition is prepared by combining (i) isocyanate, and (ii) acopolymer that is a polyol that comprises PFPE, polysiloxane, or bothPFPE and polysiloxane, and, optionally, further adding (iii) unmodifiedpolyol.

Usually polyurethane is prepared using polyol as one of the crosslinkingagents; however, it is known that polyurethane can be made usingpolyamine instead of polyol. That is, it can be prepared by combiningdiisocyanate and polyamine. The inventors envision that an amphiphobiccoating composition may be prepared by combining (i) diisocyanate, and(ii) a copolymer that is a polyamine that comprises PFPE, polysiloxane,or both PFPE and polysiloxane, and, optionally, further adding (iii)polyamine. For simplicity, the discussion herein focuses on a modifiedpolyol that bears PFPE, polysiloxane, or both. However, it is possibleto prepare a corresponding composition using a modified polyamine thatbears PFPE, polysiloxane, or both. The inventors also envision using acombination of polyol and polyamine with the copolymer “(ii)”.

In embodiments of this invention, a method of preparing component (ii)is described. This copolymer component comprises a moiety (e.g., PFPE,polysiloxane) that confers amphiphobic properties on the product coatingcomposition. In certain embodiments of the invention, such moieties arecharacterized by having a glass transition temperature in a particularrange. Specifically, a PDMS-bearing copolymer has a glass transitiontemperature in the range of −60° C. to −150° C. A PFPE-bearing copolymerhas a glass transition temperature in the range from −160° C. to −10° C.In certain embodiments, polyurethane-based coating composition preparedby these described methods have 1 to 40 wt % fluorine and/or 1 to 40 wt% siloxane.

Two different approaches have been developed for incorporating PFPEand/or siloxane into such polyurethane (PU)-based amphiphobic coatingcompositions. The two approaches have been labelled Approach “A” forpreparing component (ii) as a randomly grafted copolymer, and Approach“B” for preparing component (ii) as a block copolymer with a randomblock. The location of the PFPE or polysiloxane moieties is the keydifference between these Approaches. Specifically, for the blockcopolymers, the PFPE or polysiloxane is added at one end of thecopolymer's backbone. For the grafted copolymer, the PFPE orpolysiloxane is located randomly at side chain positions along thecopolymer. These approaches are discussed further below. Detailsregarding making clear coatings are provided in the Working Examples.Importantly, coatings have been made from solutions that include avariety of solvents. In some embodiments the coating is obtained from asolution of both a hydrophobic solvent and a water-miscible solvent. Insome embodiments the hydrophobic solvent is used to solubilize themixture, and then a water-miscible or aqueous solvent is added, and thehydrophobic solvent is removed. Examples of hydrophobic solvents includeketone such as acetone or ethylmethylketone, THF, ester such as ethylacetate, or 1,2-dimethoxyethane. Examples of water-miscible solventsinclude acetonitrile or dimethyl carbonate.

When such PFPE or polysiloxane-bearing copolymers are added toisocyanate, and, optionally, unmodified polyol is also added, theresultant polyurethane-based coating is optically clear (i.e.,transparent), durable, and resistant to both oil and water. Proof ofsuch oil- and water-resistance is described herein. For example,droplets of water and droplets of oil that are in contact with suchcoatings simply slide off when the coated surface is at a sufficientlyhigh tilting angle (such as 40° for hexadecane and 80° for water). Aftersliding off, there is no trace left behind. Another example is that whena coated surface is written upon using a permanent marker, the inktraces shrink and hardly leave a mark. Any ink traces that are left canbe easily wiped off of these coatings with a dry cloth or the like. Incontrast, uncoated glass shows clear traces of permanent marker that isdifficult to remove and cannot merely be wiped off with a dry cloth. Inaddition, fingerprints are not readily deposited onto these coatings. Ifthey do become imprinted, the prints are readily removed from thesesurfaces. Additionally, the coatings are sufficiently thick to endurewear.

Water-based polyurethane was also investigated and it was possible toadd the dynamic component and make the resultant films amphiphobic.Notably, protecting groups were used on the polyisocyanate moieties toprotect them from reacting with water. See Example 18 for details.

Embodiments of the current invention are moieties that are incorporatedinto a polyurethane matrix. Such moieties exhibit dynamic chain mobilityat room temperature. In embodiments of the invention, one end of suchpolymer chains is covalently linked to the PU matrix while the other endis not linked and may move around. This chain mobility allows thesechains to migrate to the surface. Although not wishing to be bound bytheory, the inventors suggest that such free movement of chains (i.e.,dynamic chain mobility at room temperature) prevents formation ofpermanent contacts between a foreign substance (e.g., rain, ink, paint,or greasy fingerprints) and the coating. Where the coating is on asurface that is flat and is lacking solid protrusions, a liquid foreignsubstance readily slides off the coated surface. Such water and oilrepellency properties of these amphiphobic PU formulations arequantified in the working examples provided herein.

Such copolymers were investigated, one family included a fluorinatedmoiety and another family of copolymers included a polysiloxane moiety.Studies were conducted with mixtures of these moieties, with the resultthat samples having both fluorine and siloxane moieties behavedsimilarly to the fluorine-containing coatings with regard to slidingangle and contact angle. The copolymer that included fluorine was aperfluoropolyethers (PFPE). Examples of PFPEs that can be used includeKrytox, which has a T_(g) of ˜−71° C. (see Yarbrough, J. C. et al.,Macromolecules 2006, 39, 2521), Demnum, which has a T_(g) of ˜−115° C.,and Fluoro-Link, which has a T_(g) of approximately −72° C.(Organofluorine Chemistry: Principles and Commercial Applications,edited by Ronald Eric Banks, B. E. Smart, J. C. Tatlow, p. 466). Apolysiloxane that can be used is PDMS, which has a T_(g) of −125° C.(Clarson, S. J. et al., Siloxane polymers; Prentice Hall EnglewoodCliffs, N J, 1993). The chemical structures of some exemplaryperfluoropolyethers and polysiloxanes are shown below.

As introduced above, to provide water and oil repellency to PUformulations, two different approaches were used. Approach A used aPFPE-bearing or a PDMS-bearing graft copolymer. Approach B involved ablock copolymer that included a PFPE or a PDMS block. General formulasare shown below for these approaches.

Approach A provides a graft copolymer has the following general formula:

where

-   -   FS is a moiety that includes PFPE, polysiloxane, PEO, PIB, PB,        or any combination thereof, such as, for example, Krytox,        Demnum, Fluorolink D, and aflunox;    -   R is a moiety that includes a functional group (e.g., hydroxyl,        amine, imine, carboxyl, glycidyl, isocyanate, or anhydride        moieties) that is suitable for reaction with PU's main        components (e.g., isocyanate);    -   Mi is one or more than one monomer (e.g., acrylates,        methacrylates, styrenes, and vinyl esters or a combination        thereof);    -   x is a number that represents the percentage of FS moieties;    -   y is a number that represents the percentage of R moieties; and    -   n is number of repeat units.

Polysiloxane side chains that can be a part of a FS unit includespolydialkylsiloxane, where alkyl is C₁ to C₂₀, such as, for example,polydimethylsiloxane, polydiarylsiloxane, and polyalkylarylsiloxane.

Embodiments wherein the FS moiety has both PFPE and polysiloxane canexist in the form of two types of grafts incorporated into a copolymerin a statistical fashion. Alternatively, PFPE and polysiloxane moietiescan co-exist in a single type of graft that is incorporated onto thecopolymer. The PFPE moieties provide oil- and water-repellency to theresultant product. Similarly, polysiloxane repels oil and water becauseof its dynamic non-wetting properties.

Mi denotes one or more than one monomer that improves compatibility ofthis graft copolymer with other components of the final formulation forwhich it is being prepared. Such final formulations may be, for example,glue or paint formulations. Mi may be chosen to improve the mechanical,optical, and other properties of the final coating.

In certain embodiment, R, which is characterized by its functional group(e.g., hydroxyl, amino, carboxyl, glycidyl, isocyanate, or anhydridemoieties) may have its functional group present in a protected form.That is, the functional groups may include protecting or blockinggroups. They can include protected amino, protected isocyanate,protected carboxyl, and protected hydroxyl moieties. The functionalgroups are released (i.e., unprotected) upon exposure to heat, moistureor irradiation. By using blocking groups, it is possible to control thetemperature or readiness of the glue curing chemistry.

Approach B provides a block copolymer with a random copolymer block thathas the following general formula:

where the first block is FS, which is a polymer block that comprisesPFPE, polysiloxane, PEO, PIB, PB, or any combination thereof. As anexample of such a combination, in certain embodiments it is feasible tohave FS comprise a first polymer block that comprises PFPE moieties, anda second polymer block that comprises polysiloxane moieties.

The term “b” represents the term block, as defined above.

The second block is a random copolymer having at least two and typicallythree components. R is a monomer that comprises a reactive moiety. Thatis, R bears at least one functional group that is suitable to react withan isocyanate moiety. Such functional groups may include, for example,OH, NH₂, epoxy, or glycidyl. The functional groups can also be protectedversions of the afore-mentioned functional groups. Such protectinggroups are released upon heating or upon exposure to moisture or uponexposure to irradiation. Such release exposes an unprotected functionalgroup, which leads to reaction. By using these “blocking” groups, onecan control the temperature at which the polymer mixture cures.

y is a number that represents the percentage of R moieties; Mi denotesone or more than one monomer that is incorporated to improvecompatibility of this random copolymer with other components of thefinal formulation for which it is being prepared. Such finalformulations may be, for example, glue or paint formulations.Furthermore, Mi are chosen to improve the mechanical, optical, and otherproperties of the final coating. Examples of Mi include acrylates,methacrylates, styrenes, and vinyl esters.

n is number of repeat units.

While we have so far emphasized the modification of the polyol componentusing PFPEs and polysiloxanes, the inventors have also shown that onecan also modify the polyisocyanate component of a PU formulation andleave the diol or polyol component alone (see Example 43). If onechooses to modify the polyisocyanate component, the isocyanate componentshould have more than two isocyanate groups per molecule so that one ormore PFPE or polysiloxane chains can attach to a polyisocyanate moleculewithout reducing its isocyanate group number below 2.

Methods of how to make clear coatings that are amphiphobic andanti-smudge are described more fully in the Working Examples. Briefly,the methods include the following techniques.

Combine the following to form a mixture: (i) a copolymer that is apolyol that comprises a polysiloxane moiety, (ii) di-, tri- orpoly-isocyanate, and, (iii) a first solvent (e.g., acetone) thatsolvates the mixture; heating, optionally, adding (iv) a polyol thatdoes not comprise a polysiloxane moiety, and continuing to apply heat,cooling; adding a second solvent (e.g., acetonitrile, DMF, ordimethylcarbonate) that selectively solvates a portion of the mixture,the solvated portion being that which is not the polysiloxane moiety;removing the first solvent under reduced pressure; adding additionalsecond solvent to form a coating solution; dispensing the coatingsolution onto a surface of a substrate; drying the coated substrate; andcuring the coating. Curing may involve heating, adding a curing catalyst(e.g., a tertiary amine, Dibutyltin dilaurate) or both heating andadding a curing catalyst.

Combine the following to form a mixture: (i) a copolymer that is apolyol that comprises a PFPE moiety, (ii) di-, tri- or poly-isocyanate,and, optionally, adding (iii) a polyol that does not comprise a PFPEmoiety, and adding a solvent (e.g., tetrahydrofuran) that solvates aportion of the mixture, the solvated portion being that which is not thePFPE moiety, to form a coating solution; applying the coating solutiononto a surface of a substrate; drying the coated substrate; curing thecoating.

Combine in any order (i) a polyol and/or a polyamine, (ii) di-, tri- orpoly-isocyanate; and (iii) an additive that is a copolymer thatcomprises a siloxane moiety.

Combine (i) a polyol, and (ii) an additive that is a copolymer thatcomprises a siloxane moiety to form a mixture, and add (iii) di-, tri-or poly-isocyanate to the mixture.

Combine (i) a polyamine, and (ii) an additive that is a copolymer thatcomprises a siloxane moiety to form a mixture, and add (iii) di-, tri-or poly-isocyanate to the mixture.

Combine (i) a polyol and/or a polyamine, and (ii) poly-isocyanate thatcomprises a siloxane moiety. Item (ii) can be a product of reaction ofdi-, tri- or poly-isocyanate and an additive that is a copolymer thatcomprises a siloxane moiety (an example additive ispolysiloxane-b-poly(glycidyl methacrylate))

Specifically, FIG. 1 graphically demonstrates the relationship betweensliding angle and weight percentage of fluorine for PU films preparedfrom Example 1B(i). FIG. 2 graphically demonstrates the relationshipbetween percentage transmittance versus fluorine content for PU filmsprepared from Example 1A(i). FIG. 3 graphically shows variation in thesliding angles vs. NCO/OH ratio. Solid lines show sliding anglesmeasured before a rubbing test, while dotted lines denote sliding anglesmeasured after a rubbing test. Rubbing tests were performed using a 400g weight for 40 min at 40 rpm. The sliding angle tests were performedusing 20 μL water droplets and 5 μL hexadecane droplets. FIGS. 4a-d showphotographs of artificial fingerprint impressions that were applied onto(a) ordinary glass; (b) glass coated with coating of Example 1A(i); (c)glass coated with coating of Example 1A(ii); and (d) glass coated withcoating of Example 1C(ii). FIG. 4a shows a deep pattern on uncoatedglass, indicating the easy acceptance of the smudge by uncoated glass.FIGS. 4b and 4c show dim patterns where the liquid has beaded-off intoballs indicating anti-smudge properties. FIG. 4d shows a pattern that isbetween uncoated glass (FIG. 4a ) and FPU coated glass (FIGS. 4b and 4c), indicating the antismudge properties that are better than ordinaryglass. FIG. 5 demonstrates the clarity of films described herein byshowing percentage transmittance versus wavelength observed for (a)uncoated glass; (b) unmodified drop cast polyurethane films; (c) PFPE PUfilms prepared from Example 1B(i); (d) PFPE PU films prepared fromExample 1A(i); (e) PFPE PU films prepared from Example 1A(ii); (f) spincoated PFPE PU film just a few nm in thickness prepared from Example1B(i); (g) spin coated PFPE PU film just a few nm in thickness preparedfrom Example 1A(i); and (h) spin coated PFPE PU film just a few nm inthickness prepared from Example 1A(ii). All spin coated samplesexhibited high % T values showing clear films that are transparent.

FIG. 6 shows an anti-ink test performed at the junction of uncoatedglass and coated glass. Various coated samples that had been marked witha permanent marker (top row) and were subsequently cleaned via wiping(bottom row). Coating were as follows: a) unmodified PU bearing markerline; b) PFPE PU films prepared from Example 1A(i) bearing marker lineon coated glass to the left of the arrow, and bearing marker line onuncoated glass to the right of the arrow (notably, on the coated glassthe marker ink is unable to form a line but instead appears as smallround balls of ink); c) PFPE PU films prepared from Example 1B(ii)bearing marker line on coated glass to the left of the arrow, andbearing marker line on uncoated glass to the right of the arrow(notably, on the coated glass the marker ink is unable to form a linebut instead appears as small round balls of ink); a1) unmodified PUafter wiping; b1) Example 1A(i) PFPE PU after wiping which shows thatthe ink that was on the coated glass (left of arrow) has wiped awaycompletely, while the ink on the uncoated glass (right of arrow)remains; c1) Example 1B(i) PFPE PU after wiping which shows that the inkthat was on the coated glass (left of arrow) has wiped away completely,while the ink on the uncoated glass (right of arrow) remains. FIG. 7shows a schematic representing formation of PFPE PU films.

Epoxy-Based Coatings

Transparent anti-smudge coatings were achieved by incorporating epoxyresin with polymers having a low Tg such as, for example, polysiloxaneand fluorinated moieties. Advantages of incorporation of such moietiesinto epoxy coatings include good performance regarding repulsion of oiland water, and retention of good optical clarity. Due to complicationssuch as macro phase separation, it is not possible to simply blendpolysiloxane polymers or polyfluorinated polymers into epoxy resins toprepare such coatings. Methods have been developed to overcome suchchallenges and are described in the Working Examples.

An optically-clear, amphiphobic, and durable epoxy coating compositionhas been prepared and its properties have been quantified. Thiscomposition is prepared by adding a new component to the traditionalepoxy formulation of epoxy resin and hardener. The new component is adynamic polymer that is bound at one end and is free at the other end.In some embodiments, such dynamic polymers include polydimethylsiloxane(“PDMS”) and/or PFPE. FIG. 10 shows a schematic overview of thisincorporation.

In step 1 of FIG. 10, a polymer (P10″), bearing functional moieties isreacted with a PDMS- or PFPE-bearing reactant. P10 bears functionalgroups that are any groups that are involved in epoxy resin curing,examples of such functional moieties include amine, imine, hydroxyl,carboxyl, anhydride, etc. In this first reaction, PDMS or PFPE moietiesare added to P10 to form a second polymer (“P20”). Structural formulaeof representative examples of P20 polymers are shown in the Figures, andin the Working Examples.

In step 2 of FIG. 10, P20 was mixed and reacted with an excess ofepoxide resin which typically bears one or more glycidyl groups to forma third polymer (“P30”), which bears epoxide moieties and either PDMS orPFPE.

In step 3, P30 was then mixed with a hardener (also known as anactivator) and optionally solvent (or mixture of solvents).

The resultant mixture that included P30, hardener, and optionally asolvent was then coated on a substrate (e.g., a glass plate) and thecoated film was cured after the solvent was fully evaporated. Theresulting coating was clear, durable and repelled both oil and water.Effectively, it was smudge-proof and liquid-proof. Any residue that wasdeposited could be readily removed, for example by wiping lightly with adry cloth.

Weight percentage (wt %) of PDMS/PFPE can be controlled by blendingdifferent amount of P20 into epoxy resin. Samples with PDMS/PFPO wt % of1.0%, 5.0%, 8.0% and 12% all were shown to repel both oil and water.Coating of different thickness were tested ranging from about 1 μm toabout 1 mm. It was determined that thickness did not affect therepellency.

The amphiphobic epoxy coatings described herein can be prepared using avariety of types of epoxy resins. An example of a suitable epoxy resinis bisphenol A diglycidyl ether epoxy resin (Bis-A).

A hardener (also called activator) that is suitable for reaction with anepoxy resin, or a mixture of resins, comprisespoly(oxypropylene)diamine, nonylphenol, triethanolamine and piperazine.The compositions containing piperazine are fast curing when heated toabout 120° C., with a fully cured time that is usually less than threedays at room temperature. Hardener content can be about 1 to 1 parts byvolume of bisphenol A diglycidyl ether epoxy resins.

Several PDMS- and PFPO-modified functional polymers (P20) were preparedas described in the working examples. Methods of making and using suchcompositions are also described herein.

The amphiphobic coatings described herein exhibited good opticalclarity. Transmittance tests of coatings of different thickness and PDMSwt % indicated that increasing PDMS wt % in the film reducedtransmittance. Without wishing to be bound by theory, the inventorssuggest that the decrease in transmittance is due to the increase insegregated PDMS nanodomains in the epoxy resin matrix, A 25.3 μm thickfilm with a PDMS wt % of about 9.2% gave 98.7% transmittance. FIG. 18shows a repellency test, wherein PDMS wt % is as low as about 2.6% wasenough to provide good anti-smudge properties; at this PDMS wt %, a 28.8μm thick film exhibited 99.5% transmittance.

When such epoxy coatings that include PFPO or polysiloxane-bearingmoieties were prepared, the resultant coating were optically clear(i.e., transparent), durable, and resistant to both oil and water. Proofof such oil- and water-resistance is described herein. FIG. 19graphically shows data regarding the contact angles versus wt % of PDMS.Contact angles (CTA) for water and for oil (e.g., hexadecane) on anamphiphobic epoxy film of about 101° and about 28°, respectively. Valuesof CTA changed only slightly with PDMS wt %. This means even a low PDMSaddition would change surface properties.

Even though CTA measurement shows the films are hydrophobic andlipophilic, sliding angle studies show that 5-μL oil (i.e., hexadecane)in a droplet slides off at a tilt angle of about 3°. This is so evenwhen the PDMS wt % is as low as 2.6%. See FIG. 20 for data regardingsliding angle. A 15-μL water droplet slides off with no trace left, whenthe tilt angle is about 60.5° when PDMS wt % is 2.6%.

Although amphiphobic epoxy-based coating and/or adhesive compositionsthat are two-pack epoxy formulations are described and exemplifiedherein, it is possible to have single-pack formulations. That is, theinventors envision that functional groups of the hardener could be in aprotected form. Examples of such protected functional groups may includeprotected amino, protected hydroxyl, protected carboxyl, or protectedthiol groups. In protected form, the hardener and epoxy components canbe mixed and stored in one pack. Upon the application of an externalstimulus such as heating or irradiation, the functional groups becomedeprotected and are released. Subsequently, the epoxide-ring-openingreactions occur. Such single-pack formulations are stable at roomtemperature. Curing occurs when the components are heated or irradiated.

The inventors also envision preparation of a water-dispersibleformulation for epoxy coatings. In this case, the epoxy part and thehardeners are dispersed in water. Ring-opening reactions take placeafter water has been evaporated and a pre-curing film has been formed.In the case of a single-pack water-based formulation, an externalstimulus (e.g., heat or irradiation) are applied only after thepre-curing film has formed.

These coatings have applications for the protection of hand-heldelectronic devices to reduce the accumulation of fingerprints andsmudges. They are also useful when applied to automobile windshields orwindows of high-rise buildings to reduce the need for cleaning. They caneven be used as a protective overcoat or to protect internal structuresin automobiles. When used as the top coat of architectural or industrialcoatings in sensitive areas, they provide graffiti resistance. Suchgraffiti resistance can be useful for sensitive or often-targeted areassuch as shipping containers, railcars, building materials (e.g.,concrete, aluminum siding, glass, wood, metal, flooring, marble, stone,tile). They can also be used as the coatings for moulds (such as, forexample, those used in plastic industry) to facilitate release of moldedobjects. They can be used to coat surfaces to reduce ice deposition,such as, for example, surfaces of wind turbines, airplane parts, etc.Such oil- and water-repellent coatings can be used to facilitate cleanupor simplify production of food products. They may be used to coat theinterior of oil pipelines to reduce deposition and friction.

These clear compositions would be useful in a paint or any other type ofcoating. The amphiphobic properties mean that surfaces coated with suchcoatings would display anti-smudge, and anti-graffiti properties. Greasyfingerprints would not adhere to a coated surface. If they did, thesmear could be wiped away easily with a dry cloth or the like. Suchclear anti-smudge coatings would be an asset to eyeglasses, electronicdevices, windows, screens, cell phones, tablets, electronic devices,equipment that is exposed to dirt and grime, hand-held electronicdevices, windows of high-rise buildings, automobile bodies, windshields.

Amphiphobic polyurethane-based and epoxy-based films have been preparedusing PFPE and PDMS. Such films, with a thickness ranging from a few nmto about 10 μm, have been prepared and showed water and oil repellentproperties. Both water and hexadecane readily slide off these surfaceswithout leaving any traces. These films are optically clear with >90 T%. FPU or PDMSPU films ranging in thickness from about 500 nm to about 2μm exhibited better transmittance properties than thicker films.Similarly, fluorinated epoxy films and PDMS-epoxy films exhibitedexcellent transmittance. See, for example, in FIG. 18 a transmittance ofapproximately 99% for a film thickness of 25 μm for 4.8 wt % of PDMS,and in FIG. 23 a transmittance of 99% for a film thickness of 24 μm for4.0 wt % of PDMS. Therefore, these films are suitable for applicationswhere optically clear coatings are required.

The amphiphobic films are durable against abrasion. These films weresubjected to rubbing tests against forces of 1-5 N from 800 to 4800cycles, which did not cause any significant changes in the properties ofthese films. The films remained in as good shape as before the rubbingtest.

Another feature of these films is their ink-resistance. Permanent markerleaves only a faint line, which immediately shrinks into tiny droplets.Though the permanent marker ink undergoes shrinkage after drying, it iseasily wiped away with a dry cloth.

The amphiphobic films were resistant against fingerprints and smudges asverified by a stamp-test using liquid that simulates finger prints. Thecoatings helped to minimize the probability of contamination ofsurfaces.

The amphiphobic films exhibited strong adhesion to glass surfaces.Consequently, these films can be readily applied onto these substratesand other substrates to yield durable films.

PU coatings prepared by Approach A and using PFPE have shown excellentperformance particularly at low (12% PFPE) grafting densities. Thiseffectiveness at low grafting densities can help minimize the need forfluorinated materials.

Interestingly, particles can be embedded into the polyurethane-basedcoating composition. As an example of such embedding, silica particleshave been successfully embedded in an example coating as described inExample 15. Other particles that could be embedded include silica,titanium dioxide, diatomaceous earth, alumina, TiO₂, and/or pigments.

Other compounds that can be added to the polyurethane-based amphiphobiccoating compositions include biocides. By including biocides, coatingsmay prevent accumulation of organisms (e.g., bacteria, algae, fungi,mollusks, arthropods). In various embodiments an organism may comprise amicroorganism. The microorganism may be a Gram-negative bacteria orGram-positive bacteria.

The coatings are applicable to fabrics and other solids other than glassto prepare optically clear, stain-resistant, and smudge-free surfaces.Also, the coating can be used for irregular geometrical solids as wellas rough surfaces.

The coatings described herein can be applied by all traditional coatingmethods including solution casting, brushing, aero-spraying, painting,printing, stamping, rolling, dipping, wiping, sponging, spin-coating,spraying, electrostatic spraying and/or dip-coating.

Amphiphobic coatings may also be permanent or temporary, depending onmethods used for application onto a substrate. In general, curing orannealing a coating onto a substrate (e.g., by heating or exposing toUV) will provide a permanent coating which is durable, as definedherein. Alternatively, certain coatings applied without curing orannealing may be temporary, removable and/or short-lived, since chainsthat are not crosslinked or covalently attached to a substrate may belost due to surface scratching or may be rinsed away by solvents orwater.

A variety of substrates can be coated using amphiphobic copolymersdescribed herein, including but not limited to plastics, metal oxides,semi-conductor oxides, metals, metalloids, metal oxides, concretes, clayparticles, sand particles, cement particles, saw dust, semiconductors,particles, glasses, ceramics, papers and textile fibers. In someembodiments surfaces to be coated are in the form of metal plates, metalsheets or metal ribbons. In some embodiments, substrates are particles.For example, amphiphobic copolymers of the invention may be coated ontoparticles, and the coated particles may then be used for coating anothersubstrate.

Many applications are anticipated for amphiphobic surfaces and coatings.For example, buildings (e.g., skyscrapers) with amphiphobic walls wouldrequire no or minimal cleaning. Ice would not likely form or build up onamphiphobic surfaces of power cables, which can minimize damage fromfreezing rain or ice storms. Amphiphobic coatings on metal surfaces canreduce metal rusting and corrosion. Amphiphobic coatings can be used toproduce paper and paperboard for food-contact applications, such aspizza boxes and sandwich wraps. Amphiphobic coatings may be used toprepare glasses and ceramics that are self-cleaning, or to providearc-resistant coatings on insulators used in electrical transmissionsystems where dirt or salt deposits, alone or in combination with water,can allow arcing with significant electrical energy losses. For cementand masonry products, amphiphobic coatings can provide products andsurfaces resistant to damage in freezing weather from water that haspenetrated the surfaces. As another example, amphiphobic coatings can beused to prepare paper products and fabrics which are resistant to waterand moisture, including, but not limited to: paper and fabric moisturebarriers used for insulation and under shingles or roofing; cardboardtubes or pipes, for example used to cast concrete pillars (waterpenetrating the seams of such tubes can leave seams and other defects inthe pillars that need to be fixed by grinding operations); andwater-resistant paper and cardboard packaging. Amphiphobic coatings canbe used to prepare products which are salt-water-resistant, for examplefor underwater applications such as ship hulls, submarines, and othermarine applications.

In some embodiments, amphiphobic coatings described herein can be usedto prepare surfaces which are anti-wetting, anti-icing, anti-corrosion,anti-rust, anti-scratching, anti-staining, anti-bacterial, abrasionresistant, anti-fingerprint marking, anti-smudging, anti-graffiti,acid-resistant, base-resistant, resistant to chemicals, resistant toorganic solvents, resistant to etching and/or self-cleaning. Surfacescoated with copolymers described herein may resist spills, resiststains, resist soiling, release stains, have improved cleanability, haveimproved alkaline resistance, have improved acid resistance, haveimproved resistance to organic solvents, have improved resistance tochemical penetration (e.g., improved resistance to organic chemicals),have improved resistance to corrosion, and/or have improved durabilitycompared to uncoated surfaces.

To demonstrate anti-graffiti properties using oil-based paints andpermanent black marker, FIGS. 24a-h contrast unmodified “regular” epoxycoatings with a representative example modified epoxy coating,specifically PEI-g-PDMS modified epoxy coatings having 4.0 wt % PDMS.FIG. 24a shows an unmodified coating on a vertically-positioned glassslide after an oil-based spray paint (“Paint A”) has been sprayed on it.In regard to details regarding the paint, its label lists acetone,toluene, propane, butane, ethyl 3-ethoxypropionate, dimethyl carbonateas solvent mixture. Excellent anti-graffiti properties are demonstratedin FIG. 24b which shows the modified epoxy coating on avertically-positioned glass slide after Paint A has been sprayed on it;notice how the paint has slid off to the bottom. FIG. 24c shows theunmodified coating on a vertically-positioned glass slide after oilbased spray Paint B had been sprayed on it. FIG. 24d shows the modifiedepoxy coating on a vertically-positioned glass slide after Paint B hadbeen sprayed on it; notice how the paint has slid off to the bottom.FIG. 24e shows a glass slide bearing unmodified coating after apermanent black marker has been used to draw a black mark on it, FIG.24f shows a glass slide bearing modified coating after a permanent blackmarker has been used to draw a black mark on it, note that the ink doesnot stick and has formed little balls of ink on the surface. FIG. 24gshows the same slide as 24 f when a portion of the marker mark has beenwiped with a dry tissue. To demonstrate durability of the modified epoxycoating, FIG. 24h shows a glass slide bearing modified coating after arubbing test was conducted for 18 hours (see Example 6 for details),following the rubbing, a black marker has been used to draw a black markon it, note that the coating has exhibit good durability and the inkdoes not stick.

In some embodiments, amphiphobic coatings described herein can be usedto prepare plastic or glass surfaces which are smudge-resistant, scratchresistant and/or stain resistant. Such plastic and glass surfaces may befound, for example, on electronic devices. Electronic devices can beportable (e.g., cellular phones; smartphones (e.g., iPhone™,Blackberry™); personal data assistants (PDAs); tablet devices (e.g.,iPad™); game players (e.g., PlayStation Portable (PSP™), Nintendo™ DS);laptop computers; etc.), or not portable (e.g., computer monitors;television screens; kitchen appliances; etc.).

In some embodiments, amphiphobic coatings described herein providesurfaces which are highly water- and oil-repellant. Contact angle ofwater and/or oil on a coated surface or material may be about 90 degreesor greater, about 100 degrees or greater, about 110 degrees or greater,about 120 degrees or greater, about 130 degrees or greater, about 150degrees or greater, about 90 degrees, about 110 degrees, about 120degrees, about 150 degrees, about 160 degrees, or about 170 degrees. Itshould be understood that contact angles cannot be greater than 180degrees, which is the theoretical maximum angle possible.

In further embodiments, amphiphobic coatings described herein providesurfaces which resist adhesion of biological materials. For example,anti-adherent surfaces comprising amphiphobic copolymers of theinvention are provided which repel proteins, bacteria, dirt, grime,soil, fungi, viruses, microbes, yeast, fungal spores, bacterial spores,gram negative bacteria, gram positive bacteria, molds and/or algae. Suchsurfaces may also resist adherence of biological or bodily fluids suchas blood, sputum, urine, feces, saliva, and/or perspiration/sweat. In aparticular embodiment, amphiphobic coatings reduce or preventmicroscopic animals such as dust mites and bedbugs from colonizing inmattresses, bedding, upholstery and/or carpeting.

Amphiphobic coatings, or particles coated with amphiphobic copolymers ofthe invention, can be applied to any surface to which an amphiphobiccopolymer of the invention can adhere, either temporarily orpermanently. The surfaces may be flexible or rigid. In some embodimentsa surface can be made from a material which is fabric, glass, metal,metalloid, metal oxide, ceramic, wood, plastic, resin, rubber, stone,concrete, a semiconductor, a particle or a combination thereof. In someembodiments, surfaces may comprise metalloids (e.g., B, Si, Sb, Te andGe).

Any glass can be employed as a substrate for amphiphobic coatingsaccording to the invention, including, without limitation: soda limeglass, borosilicate glass, sodium borosilicate glass, aluminosilicateglass, aluminoborosilicate glass, optical glass, fiberglass, leadcrystal glass, fused silica glass, germania glass, germanium selenideglass, and combinations thereof.

Any metal can be employed as a substrate for amphiphobic coatingsaccording to the invention, including, without limitation: iron, nickel,chrome, copper, tin, zinc, lead, magnesium, manganese, aluminum,titanium silver, gold, platinum, and combinations thereof, or alloyscomprising those metals. Metal oxides may also be present in thesubstrates. In one embodiment, a metal forming a surface comprises steelor stainless steel. In another embodiment, a metal used for a surface ischromium, is plated with chromium, or comprises chromium or a chromiumcoating.

Any ceramic can be employed as a substrate for amphiphobic coatingsaccording to the invention, including, without limitation: earthenware(typically quartz and feldspar), porcelain (e.g., made from kaolin),bone china, alumina, zirconia, and terracotta. For the purpose of thisdisclosure, a glazing on a ceramic may be considered either as a ceramicor a glass.

Any wood can be employed as a substrate for amphiphobic coatingsaccording to the invention, including, without limitation, hard and softwoods. In some embodiments, woods may be selected from alder, poplar,oak, maple, cherry, apple, walnut, holly, boxwood, mahogany, ebony,teak, luan, and elm. In other embodiments woods may be selected fromash, birch, pine, spruce, fir, cedar, and yew.

Any plastic or resin can be employed as a substrate for amphiphobiccoatings according to the invention, including, without limitation,polyolefins (such as a polypropylene and polyethylene),polyvinylchloride plastics, polyamides, polyimides, polyamideimides,polyesters, aromatic polyesters, polycarbonates, polystyrenes,polysulfides, polysulfones, polyethersulfones, polyphenylenesulfides,phenolic resins, polyurethanes, epoxy resins, silicon resins,acrylonitrile butadiene styrene resins/plastics, methacrylicresins/plastics, acrylate resins, polyacetals, polyphenylene oxides,polymethylpentenes, melamines, alkyd resins, polyesters or unsaturatedpolyesters, polybutylene terephthlates, combinations thereof, and thelike.

Any rubber can be employed as a substrate for amphiphobic coatingsaccording to the invention, including, without limitation: naturalrubber, styrene-butadiene rubber, butyl rubber, nitrile rubber,chloroprene rubber, polyurethane rubber, silicon rubber, and the like.

Any type of stone, concrete, or combination thereof can be employed as asubstrate for amphiphobic coatings according to the invention,including, without limitation, igneous, sedimentary and metamorphicstone (rock). In one embodiment the stone is selected from granite,marble, limestone, hydroxylapatite, quartz, quartzite, obsidian andcombinations thereof. Stone may also be used in the form of aconglomerate with other components such as concrete and/or epoxy to forman aggregate that may be used as a surface upon which an amphiphobiccoating may be applied.

Non-limiting examples of types of coatings which may be prepared usingamphiphobic coatings and methods described herein include: fabriccoatings, textile coatings, decorative coatings, transportationcoatings, wood finishes, powder coatings, coil coatings, packagingfinishes, general industrial finishes, automotive paint (includingrefinishing paint), industrial maintenance and protective coatings,marine coatings, and other industrial coatings.

Non-limiting examples of applications of these types of coatingsinclude: furniture (e.g., wood and metal furniture, outdoor furniture,office or commercial furniture, fixtures, casual furniture); motorvehicles; metal building components; industrial machinery and equipment;appliances (e.g., kitchen appliances, laundry appliances); aerospaceequipment; packaging (e.g., interior and exterior of metal cans,flexible packaging, paper, paperboard, film and foil finishes);electrical insulation coatings; consumer electronic products (e.g., cellphones, tablet devices, MP3 players, cameras, computers, displays,monitors, televisions, hearing aids); coil coatings (e.g., coils,sheets, strips, and extrusion coatings); automotive refinishing (e.g.,aftermarket repair and repainting); industrial settings (e.g.,protective coatings for interior and exterior applications); routinemaintenance to protect buildings (e.g., protection from corrosivechemicals, exposure to fumes, and temperature extremes) or solar panels;process industries (e.g., protection from corrosive or highly acidicchemicals); roads and bridges; shipping containers and railcars; andmarine applications (e.g., boats, antifouling, ice resistance, equipmentanticorrosion). It is apparent from these examples that coatings may beapplied to articles pre-market, i.e., before, during or aftermanufacturing and before sale, or post-market, e.g., for maintenance andprotective uses.

Coatings described herein can be applied to surfaces using any meansknown in the art, including but not limited to, brushing, painting,printing, stamping, rolling, dipping, wiping, sponging, spin-coating,spraying, or electrostatic spraying. Generally, surfaces are rigid orsemi-rigid, but surfaces can also be flexible, for example in theinstance of wire and tapes or ribbons.

Coatings described herein can be applied to virtually any substrate toprovide amphiphobic properties. Choice of coating forms and processesfor applying coatings are determined by a skilled artisan, based onfactors such as chosen substrate, application, etc. Coatings may takeany desired shape or form. In some embodiments, a coating completelycovers a surface. In other embodiments, coatings cover only a portion ofa surface, such as one or more of a top, side or bottom of an object. Inone embodiment, a coating is applied as a line or strip on asubstantially flat or planar surface. In such an embodiment, the line orstrip may form a spill-resistant border.

Shape, dimensions and placement of coatings on surfaces can becontrolled by a variety of means including the use of masks which cancontrol not only portions of a surface that receive a coating, but alsoportions of a surface that may receive prior treatments such asapplication of a primer layer or cleaning by abrasion or solvents. Forexample, sand blasting or chemical treatment may be used to prepare aportion of a surface for coating, e.g., to generate desired surfaceroughness or to clean a surface. Where a portion of a surface isprepared in this way, a mask resistant to those treatments would beselected (e.g., a mask such as a rigid or flexible plastic, resin, orrubber/rubberized material). Masking may be attached to a surfacethrough use of adhesives, which may be applied to a mask agent, asurface, or both.

In another embodiment a coating is applied to a ribbon, tape, or sheetthat may then be applied to a substrate by any suitable means includingadhesive applied to the substrate, the ribbon, tape, or sheet, or acombination thereof. Ribbons, tapes and sheets bearing an amphiphobiccoating may be employed in a variety of applications, including formingspill-proof barriers on surfaces. Such ribbons, tapes, and sheets can beapplied to any type of surface including metal, ceramic, glass, plastic,or wood surfaces, for a variety of purposes.

In some embodiments, coatings may be used to form a border on a surface.An amphiphobic “border” is a portion of a surface forming a perimeteraround an area of the surface that has lower amphiphobicity than theborder. Amphiphobic borders can prevent water and other liquids fromspilling, spreading or flowing beyond the position of the border. Aspill-resistant border could be prepared, for example, by applying anamphiphobic coating to a portion of a surface (with or without use of amask), or by applying a tape or a ribbon to a surface, where one surfaceof the tape or ribbon is treated with an amphiphobic coating.

To improve adherence of coatings to a surface, a surface may be treatedor primed, such as by abrasion, cleaning with solvents or application ofone or more undercoatings or primers. In some embodiments where metalscan be applied to surfaces (e.g., by electroplating, vapor deposition,or dipping) and it is deemed advantageous, surfaces may be coated withmetals prior to application of a coating described herein.

As discussed above, a wide variety of articles may be coated withamphiphobic block copolymers of the invention. Non-limiting examples ofsuch articles include metal plates, metal sheets, metal ribbons, wires,cables, boxes, insulators for electric equipment, roofing materials,shingles, insulation, pipes, cardboard, glass shelving, glass plates,printing paper, metal adhesive tapes, plastic adhesive tapes, paperadhesive tapes, fiber glass adhesive tapes, boats, ships, boat hulls,ship hulls, submarines, bridges, roads, buildings, motor vehicles,electronic devices, machinery, furniture, aerospace equipment,packaging, medical equipment, surgical gloves, shoe waxes, shoepolishes, floor waxes, furniture polishes, semiconductors, solar cells,solar panels, windmill blades, aircraft, helicopters, pumps, propellers,railings, and industrial equipment.

In some embodiments, a coated article's breathability, flexibility,softness, appearance, feel and/or hand is substantially the same as thatof an uncoated article.

In some embodiments, a coated article has improved cleanability,durability, water-repellence, oil-repellence, soil-resistance,biological species-resistance, bodily fluid-resistance, ice-resistance,salt-resistance, salt-water-resistance, acid-resistance,base-resistance, stain-resistance, organic solvent-resistance,flame-resistance, anti-fouling properties, anti-bacteria adhesionproperties, anti-virus-adhesion properties, anti-adhesion properties(e.g., anti-contaminant adhesion properties), anti-flow resistance(e.g., for underwater uses, swimming), anti-flame properties,self-cleaning properties, anti-rust properties, anti-corrosionproperties, anti-etching properties, anti smudge properties,anti-fingerprint properties, and/or ability to control moisture content,compared to an uncoated article.

In some embodiments, highly water and oil repellent textiles can beobtained by depositing an amphiphobic coating on fibrous substrates orfabrics. It should be understood that any fibrous substrate or fabricwhich can bind amphiphobic block copolymers of the invention may beused. Fibrous substrates according to the present invention includefibers, woven and non-woven fabrics derived from natural or syntheticfibers and blends of such fibers, as well as cellulose-based papers,leather and the like. They can comprise fibers in the form of continuousor discontinuous monofilaments, multifilaments, staple fibers and/oryarns containing such filaments and/or fibers, and the like, whichfibers can be of any desired composition. The fibers can be of natural,manmade or synthetic origin. Mixtures of natural fibers and syntheticfibers can also be used. Included with the fibers can be non-fibrouselements, such as particulate fillers, binders and the like. Fibroussubstrates of the invention are intended to include fabrics andtextiles, and may be a sheet-like structure comprising fibers and/orstructural elements. A sheet-like structure may be woven (including,e.g., velvet or a jacquard woven for home furnishings fabrics) ornon-woven, knitted (including weft inserted warp knits), tufted, orstitch-bonded.

Non-limiting examples of natural fibers include cotton, wool, silk,jute, linen, ramie, rayon and the like. Natural fibers may becellulosic-based fabrics such as cotton, rayon, linen, ramie and jute,proteinaceous fabrics such as wool, silk, camel's hair, alpaca and otheranimal hairs and furs, or otherwise. Non-limiting examples of manmadefibers derived primarily from natural sources include regeneratedcellulose rayon, cellulose acetate, cellulose triacetate, andregenerated proteins. Examples of synthetic fibers include polyesters(including poly(ethylene glycol terephthalate)), polyamides (includingnylon, such as Nylon 6 and 6,6), acrylics, polypropylenes, olefins,aramids, azlons, modacrylics, novoloids, nytrils, spandex, vinylpolymers and copolymers, vinal, vinyon, and the like, and hybrids ofsuch fibers and polymers. Leathers and suedes are also included.

Amphiphobic coated textiles may reject most pollutants (e.g.,naturally-occurring pollutants, chemical pollutants, biologicalpollutants, etc.) and are not easily soiled. They may show improvedproperties such as water resistance, soil resistance, oil resistance,grease resistance, chemical resistance, abrasion resistance, increasedstrength, enhanced comfort, detergent free washing, permanent pressproperties such as smoothness or wrinkle resistance, durability to drycleaning and laundering, minimal requirement for cleaning, and/orquickness of drying. Such textiles can be used to make, for example,contamination-free canvases, tents, parachutes, backpacks, flags,handkerchiefs, tablecloths, napkins, kitchen aprons, bibs, baby clothes,lab coats, uniforms, insignias, rugs, carpets, and ties.

In some embodiments, an advantage of amphiphobic coatings providedherein is that coatings may be thin and/or do not affect desirableproperties of a fabric such as breathability, flexibility, softness,and/or the feel (hand) of the fabric. Amphiphobic fabrics can thus beused to make clothing and apparel. For example, socks, hosiery,underwear, garments such as jackets, coats, shirts, pants, uniforms, wetsuits, diving suits and bathing suits, fabrics for footwear, and shoescan be coated. Home furnishing fabrics for upholstery and windowtreatments including curtains and draperies, bedding items, bedsheets,bedspreads, comforters, blankets, pillows or pillow coverings, fabricsfor outdoor furniture and equipment, car upholstery, floor coveringssuch as carpets, area rugs, throw rugs and mats, and fabrics forindustrial textile end uses may also be coated. Coating of materialssuch as cotton may, for example, alter properties of the cotton, such aswater/soil repellence or permanent press properties. Cotton-containingmaterials may be coated after procedures such as dyeing of the cotton.Cotton materials may be provided as a blend with other natural and/orsynthetic materials.

In further embodiments, amphiphobic coatings are used on leatherproducts, such as leather jackets, leather shoes, leather boots, andleather handbags. Amphiphobic coatings may also be used on suedeproducts.

Studies of the anti-smudge, and anti-graffiti properties of thesecoatings are presented in the figures and tables provided herein. Thefollowing working examples further illustrate the present invention andare not intended to be limiting in any respect. Those skilled in the artwill gain a further and better understanding of the present inventionand the new results and advantages thereof from the followingillustrative examples of the practice of this invention as it hasactually been carried out experimentally.

WORKING EXAMPLES

Materials

HEMA-TMS was prepared by a literature method (Hirao, A. et al.,Macromolecules 1986, 19, 1294). Copper(I) bromide (CuBr), copper(II)bromide (CuBr₂), 2,2′-bipyridine, trifluorotoluene (TFT), and methylnonafluorobutyl ether (MFBE), ethyl α-bromoisobutyrate (EBrIB), werepurchased from Sigma-Aldrich (Oakville, Ontario, Canada). EBrIB wasdistilled before use. CuCl and CuBr were sequentially washed with aceticacid and with anhydrous ethanol before they were dried in an oven undervacuum for 48 h at 30° C. Purified CuBr and CuCl were stored undernitrogen. Tetrahydrofuran (THF) was purchased from Caledon LaboratoriesLtd. (Georgetown, Ontario, Canada) and used without furtherpurification, but was dried using 3.0 {acute over (Å)} molecular sieves.Monomer 2-(perfluorooctyl)ethyl methacrylate (FOEMA) was generouslyprovided by Clariant GmbH (Burgkirchen, Germany) and was distilled undervacuum before use. Acetonitrile was passed through an alumina columnbefore use. P1, and dimeric hexamethylene diisocyanate (HDID) wereprovided by Lorama Chemicals Inc. (Milton, Ontario, Canada). In initialstudies, HDID was used. In subsequent studies HDIT, which is a trimer ofHDI, was used as the source of —NCO. Specifically, a poly(hexamethylenediisocyanate) (predominantly trimer, 65 mg, 80 wt % in butyl acetate,such as those sold under the trademarks UH80-ULTRA SYSTEM® bySHERWIN-WILLIAMS Co.) was used.

The following chemicals were purchased from Sigma Aldrich and used asreceived: poly(dimethylsiloxane) (monoglycidyl ether terminated, Mn˜5000g/mol), Poly(styrene-alt-maleic anhydride) (P(S-alt-MA), average Mn˜1,700 by GPC, maleic anhydride ˜32 wt %), polyethylenimine (PEIbranched, average Mw ˜25,000 by LS, average Mn ˜10,000 by GPC), branchedpolyethylenimine (PEI branched, average Mw ˜2000 by LS, average Mn ˜1800by GPC), 50 wt. % in H₂O), Polyethylene oxide methyl ether (Mn ˜750,2000, and 5000), Poly(propylene glycol) bis(2-aminopropyl ether) (PPG,Mn ˜230), bisphenol A diglycidyl ether(Bis-A), trimethylamine (≥99%),triethanolamine (≥99.0%), piperazine (99%), chloroform (≥99.5%), DMF(≥99.8%), acetone (≥99.5%), ethanol (≥99.8%), diiodomethane, hexadecane,dodecane, decane, octane, hexane, perfluoroocatanem, pyridine,azobisisobutyronitrile (AIBN). The following monomers were purchasedfrom Sigma Aldrich and redistilled before using: 2-Hydroxyethylmethacrylate (HEMA), styrene (S), butyl methacrylate (BMA), methylmethacrylate (MMA), azobisisobutyronitrile (AlBN).

Example 1 Synthesis of Modified Polyols Under Approach a for Use as anIngredient in Preparation of Amphiphobic Clear Coatings Example 1ASynthesis of Example 1A Copolymers, a PFPE-Grafted P1 Product UsingApproach a

Step 1Obtaining Solid P1 (from Commercial P1 Solution)

Commercial solution of P1 (5.0 mL) was precipitated from hexane (45.0mL) and centrifuged at 3900 rpm. The precipitate was dissolved in THFand precipitated from hexane:diethyl ether (1:0.1 v/v, 45.0 mL×2) andcentrifuged at 3900 rpm. ¹H NMR (in DMSO, at 400 MHz): ¹H NMR (inDMSO-d₆, at 500 MHz): δ 12.0-12.6 (br, —COOH, 1H), 7.37.3-6.8 (br,styrene ring, 5H), 4.7 (br, CH₂OH, 1H), 4.55 (br, CH₂OH, 1H), 4.3 ((br,—CH, 1H), 3.9 (br, —OCH₂, 2H), 3.85 (—OCH₂, 2H), 3.6 (br, —CH₂OH, 2H),3.5 (br, CO₂CH₃, 3H), 3.5 (br, —CH₂—OH), 3.35 (—OCH₂CH₂OH), 2.4-2.8 (br,—CH, 1H), 2.3 (br, —C(O)CH₂, 2H), 2-1.5 (br, —CH₂), 1.3-0.6 (br, —CH₃)ppm.

Step 2

Synthesis of PFPE-C(O)Cl

PFPE-COOH (5.0 g, 2.0×10⁻⁴ mol) was added into a two neck flask anddried under vacuum for 5 h at 40° C. The reaction flask was re-filledwith nitrogen gas before oxalyl chloride (COCl)₂ (2.0 mL, 2.3×10⁻² mol)added via an air-tight syringe. The temperature was increased to 70° C.and refluxed overnight at this temperature. The reaction mixture wascooled to 45° C., and placed under vacuum for at least 4 h at thistemperature to remove the residual oxalyl chloride. The resultantPFPE-C(O)Cl was obtained as a clear viscous liquid, which was dilutedwith methyl nonafluorobutyl ether (MFBE) and subsequently stored underan inert atmosphere.

Step 3

Grafting of PFPE onto P1

First, P1 (0.20 g, 0.76 mmol of OH) was dissolved in anhydrous THF (2.0mL). TFT (1 mL) was added at this stage. Subsequently, PFPE-C(O)Cl (0.48g, 0.20 mmol) (26.3% of the total OH groups are used for grafting while74% remain free) in nonafluoromethyl ether (0.545 mL) was added intothis polymer solution drop-wise over a period of 5 min. The reactionmixture was allowed to stir for at least 16 h. The reaction mixture wasthen diluted with THF (2 mL) and added slowly into hexane:ether (1 v/v,45.0 mL) and subsequently centrifuged at 3900 rpm. The resultantsupernatant was removed and the precipitate was dissolved in THF (3.0mL). A hexane: ether (1:0.2 v/v 45.0 mL) solvent mixture was added tothis solution drop-wise with occasional stirring using a vortex mixer.This precipitation procedure was repeated two more times. ¹H NMR (inDMSO:C₅F₅N (3:1, v/v) at 500 MHz): δ 7.3-6.8 (br, styrene ring, 5H), 4.5(br, CH₂OH, 1H), 4.4 (br, PFPE-CO₂CH₂, 2H), 4.3 (br, —CH—O), 3.9 (br,—OCH₂CH₂, 2H), 3.6 (br, —CH₂OH, 2H), 3.4 (CO₂CH₃, 3H), 2.5 ((br, 1Hstyrene ring), (br, —OCH₂, 2H), 2-1.5 (br, —CH₂), 1.3-0.6 (br, —CH₃)ppm.

Table 1 presents data for five samples of Example 1A having different OHgrouped end capped with PFPE, specifically, 13.6%, 16.5%, 23%, 27%, and35% were prepared and characterized.

Example 1A(i) was a fluoro-grafted product, which was prepared usingpolyol P1, and which had a fluoro density of 13.6%.

Example 1A(ii) was a fluoro-grafted product, which was prepared usingpolyol P1, and which had a fluoro density of 16.5%.

Example 1A(iii) was a fluoro-grafted product, which was prepared usingpolyol P1 and which had a fluoro density of 23%.

Example 1A(iv) was a fluoro-grafted product, which was prepared usingpolyol P1, and which had a fluoro density of 27%.

Example 1A(v) was a fluoro-grafted product, which was prepared usingpolyol P1 and which had a fluoro density of 35%.

Example 1B Preparation of a PFPE-Grafted Product Prepared by Grafting aPFPE Containing Species onto P(TFEMA-co-HEMA)

Step 1

Synthesis of Non-Commercially Available Polyol, P(TFEMA-co-HEMA), ViaATRP

P(TFEMA-co-HEMA) was synthesized according to Scheme 3. A typicalsynthetic procedure is described here as an example. EBrIB (100.1 mg,5.100×10⁻¹ mmol), TFEMA (1.96 mL, 1.35×10⁺¹ mmol, 27 equiv.), HEMA-TMS(3.0 mL, 1.35×10⁺¹ mmol, 27 equiv.), bipyridine (245 mg, 3.05 equiv.),CuCl (55.0 mg, 1.05 equiv.) and TFT (6.5 mL) were sequentially addedinto a two neck flask. The reaction mixture was subjected to fourfreeze-pump-thaw cycles before it was placed into a pre-heated oil bathat 88° C. The reaction was monitored by ¹H NMR spectroscopy at variousintervals. Once a 90% monomer conversion was reached (after 3 h), thepolymerization was terminated by purging the flask with air. The crudepolymer solution was diluted with TFT (5.0 mL), and passed over analumina column. This was followed by the addition of aqueous HCl (1 N)to obtain a solution with a pH of 2 as monitored with pH paper. Thecrude polymer solution was stirred for 30 min at rt and subsequentlyconcentrated via rotary evaporation. Meanwhile, the polymer precipitatedfrom this primarily aqueous solution. Water was decanted off and thepolymer was dissolved in THF (3.0 mL). The polymer solution wassubsequently added into hexane (45 mL) dropwise and centrifuged at 3900rpm for 5 min. The resultant precipitate was dissolved in THF (3 mL) andsubsequently precipitated from hexane:ether (1:0.2 v/v, 45 mL). Thisprecipitation procedure from hexane:ether was repeated two more times.The polymer was obtained as a white powder (2.6 g) in a yield of 52%. ¹HNMR (in DMSO at 500 MHz): δ 4.6 (br, —OCH₂CF₃, 2H), 4.2 (br, —CH₂OH,1H), 3.9 (br, —OCH₂CH₂, 2H), 3.6 (br, —CH₂OH, 2H), 2-1.7 (br, —CH₂, 2H),1.1-0.7 (br, —CH₃, 3H) ppm.

Table 2 presents data for three different P(TFEMA-co-HEMA) prepared byATRP.

Step 2

PFPE Grafting onto P(TFEMA-co-HEMA) to Prepare Example 1B

A generalized approach for the synthesis of grafted P(TFEMA-co-HEMA) isdescribed as follows. P(TFEMA-co-HEMA) (0.5 g) was dissolved in 3.0 mLof THF. This was followed by the addition of PFPE-C(O)Cl (per desireddegree of grafting). The reaction mixture was stirred overnight at rt.The solution was then diluted with THF (5 mL) and poured into awater:methanol mixture (3:1 v/v, 45 mL) and centrifuged at 3900 rpm for5 min. The precipitate was dissolved again in THF and subsequently addeddropwise into a hexane: ether (2:1 v/v, 45 mL) mixture and centrifugedat 3900 rpm for 5 min. The above precipitation procedure was repeatedtwo more times. The vol. % of ether in the hexane:ether mixtureincreased with increasing grafting density. ¹H NMR (In DMSO:C₅F₅N (3:1v/v) at 500 MHz): δ 4.6 (br, —OCH₂CF₃, 2H), 4.4 (br, PFPE-CO₂CH₂, 2H),4.0 (br, —CH₂CH₂, 2H), 3.65 (br, —CH₂OH, 2H), 3.2 (br, —CH₂OH and HOHpeak, 1H), 2-1.7 (br, —CH₂, 2H), 1.1-0.7 (br, —CH₃, 3H) ppm.

Table 3 presents data for four samples of graftedP[(TFEMA-co-(HEMA-g-PFPE)] having different fluoro densities,specifically, fluoro densities of 10% (Example 1B(i)); 16% (Example1B(ii); 24%, (Example 1B(iii), and 32% (Example 1B(iv), were preparedand characterized.

Example 1C Preparation of a PDMS-Grafted Product Under Approach A,Specifically Synthesis of PDMS Grafted P1

Step 1Synthesis of PDMS-O₂C₂(O)Cl

PDMS-OH (2.7 g, 0.58 mmol) was dried under vacuum for 2 h at 45° C. Theflask was cooled to rt and oxalyl chloride (1.0 mL, 12 mmol) was addedvia an air-tight syringe into the reaction mixture. The reaction mixturewas allowed to stir at rt for 12 h. Subsequently, the reaction mixturewas dried under vacuum at 45° C. for 3 h, thus yielding the polymer as aclear liquid in ˜100% yield.

Step 2

Synthesis of Example 1C

P1 (0.2 g, 0.76 mmol of OH) was dissolved in anhydrous THF (3.0 mL). Tothis solution, PDMS-O₂C₂(O)Cl (644 mg) was added dropwise (˜6-7 dropsper min) before the reaction mixture was stirred for 16 h. The polymersolution did not precipitate from hexane, methanol or any solventmixture. Therefore, the residual THF solvent along with the by-productHCl was removed from the sample under vacuum at 30° C. overnight. ¹H NMR(in CDCl₃, at 400 MHz): 7.37.3-6.8 (br, styrene ring, 5H), 4.3 (br,—CH—O, 1H), 4.1-4.2 (br, —OCH₂CH₂, 2H, and PDMS(CO)₂OCH₂), 3.6 (br,—CH₂OH, 2H), 3.5 (br, CO₂CH₃, 3H), 3.5 (br, —CH₂—OH), 3.35 (—OCH₂CH₂OH),2.4-2.8 (br, —CH, 1H of styrene), 2.1-1.5 (br, —CH₂), 1.3-0.6 (br, —CH₃,3H), 0.1 (br, —CH₃, 6H) ppm.

PDMS densities of 11.3% (Example 1C(i)); 13.5% (Example 1C(ii)); and15.6% (Example 1C(iii)), were prepared and characterized as shown inTable 4. Two other polymers at PDMS density were also prepared. Example1C(iv) (of 3.1 wt %) and Example 1C(v) (6.1 wt %) were prepared byfractionation of Examples 1C(ii) and 1C(iii), respectively.Fractionation was performed, for example, by dispersing Example 1C(ii)(˜550 mg) in 3.0 mL pentane. Nonafluromethyl ether (2.0 mL) was added tothis dispersion. The resultant mixture was centrifuged at 13000 rpm, aprecipitate was obtained and was vacuum dried. The dry product (210 mg)had a PDMS grafting density of 3.1% and was referred to as Example1C(iv).

Example 1D Preparation of an Acetylated Grafted Copolymer Under Approacha, Note that this Product has No Reactive Hydroxyl Groups

Synthesis of Acetylated Graft Copolymer

Hydroxyl group-bearing graft copolymers Example 1A(iii) and Example1C(ii) were reacted with acetic anhydride as described below. First theabove two polymers were dissolved in pyridine in separate vials. Aceticanhydride (in excess) was then added to these polymer solutions and thereaction mixtures were stirred at room temperature for 16 h. A flow ofN₂ gas was subsequently passed over the reaction mixture to remove thepyridine and unused acetic anhydride. The mixture was subsequentlywashed with methanol (20×4 mL). The samples were subsequently driedunder vacuum at 40° C. overnight before further use.

¹H NMR Characterization of acetylated Example 1A(i): ¹H NMR (InCDCl₃:C₅F₅N (3:1 v/v) at 500 MHz): δ 7.3-6.8 (br, —Styrene ring, 5H),4.35 (br, PDMS-CO₂CH₂, 2H), 4.2 (br, —OCH₂CH₂O, 4H), 3.9 (br, —CO₂CH₃,3H), 2.4-2.8 (br, —CH, 1H), 2.1 (br, —CH₃, 3H), 1.5 (br, —CH₂, 2H)1.3-0.6 (br, —CH₃, 3H) ppm.

¹H NMR Characterization of acetylated Example 1C(ii) (in CDCl₃, at 500MHz): 7.37.3-6.8 (br, styrene ring, 5H), 4.1-4.2 (br, —OCH₂CH₂, 2H, andPDMS(CO)₂OCH₂), 3.6 (br, —CH₂OH, 2H), 3.5 (br, CO₂CH₃, 3H), 3.5 (br,—CH₂—OH), 3.35 (—OCH₂CH₂OH), 2.4-2.8 (br, —CH, 1H of styrene), 2.1 (br,—CH₃, 3H), 2.1-1.5 (br, —CH₂), 1.3-0.6 (br, —CH₃, 3H), 0.1 (br, PDMSchains, —CH₃, 6H) ppm.

Table 5 shows the list of Example 1D polymers,

Example 2 Synthesis of Modified Polyols Under Approach B for Use as anIngredient in Preparation of Amphiphobic Clear Coatings

Block Random Copolymers

This unique class of block-random copolymer is represented by thegeneral formula:FS-b-(RyMi_(100%-y))_(n)where FS represents a moiety as described above and “b” denotes block. Rrepresents HEMA, in this example, Mi denotes styrene and MMA.

Studies were conducted using the following two different types ofcopolymers:

-   -   i. PFPE-b-P(HEMA₄₃-S₄₃-MMA₁₄) (Example 2A).    -   ii. PDMS-b-P(HEMA₅₃-S₃₃-MMA₁₃) (Example 2B).

Example 2A. Synthesis of PFPE-b-[S-HEMA-MMA], Under Approach B, which isa Fluoro-Block Polyol Product

Step 1Synthesis of the PFPE-Br Macroinitiator.

HO—(CH₂)₂OC(O)(CH₃)₂Br (0.8 g, 3.7 mmol) was added into THF (3.0 mL) andTEA (0.9 mL, 6.4 mmol) was added to this solution. Subsequently,PFPE-C(O)Cl (5.0 g, in 3 mL of MFBE, 2.08 mmol) and the reaction mixturewas stirred overnight. This reaction mixture was subsequently washedwith THF:water (1:1 v/v, 45.0 mL), and centrifuged at 3900 rpm. Theresultant product was further washed with THF:methanol (1:2 v/v, 45.0mL), and subsequently centrifuged at 3900 rpm. The product was allowedto dry under vacuum for 48 h prior to use. ¹H NMR (In CDCl₃:C₆F₆ (1:3,v/v at 300 MHz): δ 4.82 (br, PFPE-CO₂CH₂, 2H), 4.63 (br, —CH₂, 2H), 2.0(br, CH₃, 6H).

Step 2

Polymerization Using PFPE-Br as the Macroinitiator.

PFPE-Br (0.50 g, 1.9×10⁻¹ mmol), styrene (0.191 mL, 1.52 mmol, 8.0equiv.), HEMA-TMS (0.54 mL, 2.28 mmol, 12.0 equiv.), MMA (0.053 mL, 0.47mmol, 2.5 equiv.) were mixed together in 100 mL flask. Bipyridine (97mg, 3.0 equiv.), CuCl (32.5 mg, 1.0 equiv.) and TFT (2.0 mL) weresequentially added to this mixture. The reaction mixture was subjectedto four freeze-pump-thaw cycles before it was placed into a pre-heatedoil bath at 85° C. After 24 h, a ˜75% conversion was obtained and thereaction was stopped by introducing air into the reaction flask, andsubsequently diluting the sample with TFT (10 mL). The solution was thenpassed over an alumina column, which was also washed with THF (10 mL).Subsequently, HCl (1 N, pH=2.5) was added into the polymer solution,which was subsequently stirred for 20 min at rt. The samples weresubsequently diluted with THE (2 mL) and added slowly into ahexane:ether (1:0.2) solvent mixture. The turbid solution wascentrifuged at 3900 rpm. This precipitation procedure was repeated twomore times. The product was dried under vacuum at rt overnight. Thepolymer was obtained in a yield of 54%. ¹H NMR (in DMSO:C₅F₅N (3:1 v/vat 500 MHz): δ 7.3-6.8 (br, styrene ring, 5H), 4.6 (br, CH₂OH, 1H), 4.5(br, PFPE-CO₂CH₂, 2H), 4.0 (br, —OCH₂CH₂, 2H), 3.7 (br, —CH₂OH, 2H), 3.4(CO₂CH₃, 3H), 2-1.5 (br, —CH₂, 2H), 1.3-0.6 (br, —CH₃, 3H) ppm.

Example 2B Preparation of a PDMS-block polyol product, under Approach B

Step 1

Synthesis of PDMS-b-(HEMA-S-MMA)_(n)

Step 2Synthesis of PDMS-Br

PDMS-OH (1.5 g, 3.2×10-4 moles) was dissolved in THF (2.0 mL). TEA (0.45mL, 3.2×10⁻³ mol) was added to this solution before the addition of2-bromopropionyl bromide (0.24 mL, 2.22×10⁻³ mol). This reaction wasallowed to proceed for 20 h at rt. The resultant PDMS-Br wassubsequently washed with acetonitrile (10 mL×3) and centrifuged at 3900rpm after each washing treatment. The bottom layer was collected anddried under vacuum for 24 h at 30° C.

Step 3

Synthesis of PDMS-b-(HEMA-S-MMA)_(n) via the PDMS-Br Macroinitiator

PDMS-Br (0.80 g, 1.6×10⁻¹ mmol), styrene (0.2 mL, 1.28 mmol, 8.0equiv.), HEMA-TMS (0.54 mL, 1.92 mmol, 12.0 equiv.), and MMA (0.052 mL,0.4 mmol, 2.5 equiv.) were mixed together. Bipyridine (60 mg, 2.4equiv.), CuCl (17.4 mg, 1.1 equiv.), and TFT (2.0 mL) were sequentiallyadded to this mixture. The reaction mixture was subjected to fourfreeze-pump thaw cycles before it was placed into a pre-heated oil bathat 88° C. After 48 h, a 75% conversion took place. The reaction wasstopped by opening the stopper of the flask to introduce air, anddiluting the reaction mixture with TFT (10 mL). The crude polymersolution was passed over an alumina column. To this mixture was addedTHF (10 mL), before HCl (1 N) was added dropwise until ˜pH=2.5 wasreached. The acidic mixture was stirred for 20 min at rt. The sample wasdried under vacuum for 24 h at 30° C. ¹H NMR (in CDCl₃) at 500 MHz): δ7.3-6.8 (br, styrene ring, 5H), 4.1 (br, —OCH₂CH₂, 2H), 3.8 (br, —CH₂OH,2H), 3.5 (CO₂CH₃, 3H), 2-1.5 (br, —CH₂, 2H), 1.3-0.6 (br, —CH₃, 3H), 0.1(br, —CH₃(CH₃), 6H) ppm.

Example 3 Synthesis of Non-Amphiphobic Clear Coatings for ComparisonPurposes Example 3A Preparation of Unmodified PU

P1 (30.0 mg, 0.029 mmol of —OH] and HDID (7.0 mg, 0.033 mmol of NCOfunctional groups) were mixed and THF was added until the total THFvolume reached 1.3 mL. The mixture was homogenised under vortex for ˜10s. The polymer solution was then cast onto glass. The samples were airdried for 20 min, and subsequently annealed overnight at 120° C. priorto characterization. As shown in Table 6, the films did not exhibit anyhexadecane-repellent properties. Also, the water sliding angles werevery high. Table 6 presents data for characterization of the above clearcoating (which has no modified polyol). In subsequent studies, HDIT,which is a trimer of HDI, was used as the source of —NCO.

Example 3B Polyurethane (PU) Formulations

The synthesis of PU is shown in Scheme 7. During this preparation,urethane bonds were formed between OH and NCO groups under thermalcuring.

Example 4 Preparation of Durable, Amphiphobic Clear Coatings Using theAbove-Described Modified Polyols of Approaches A and B

An example FPU film preparation is described below. Example 1A(i) (6.0mg, 0.0082 mmol of OH) was dissolved in 1.3 mL of THF. To this solutionwas added unmodified polyol (30 mg in 0.3 mL THF, 0.029 mmol of OH),diisocynate (10.4 mg in 0.28 mL THF, 0,048 mmol). The finalconcentration 25.0 mg/ml in THF and NCO/OH ratio was 1.27. Thesesolutions were then drop casted on glass slides. For consistentconditions regarding humidity, the drop casted substrate was dried byplacing it in a dessicator with CaCl₂. The dessicator had an inlet andan outlet and was purged under a gentle flow of N₂. After ˜20 min, thesamples were cured overnight at 120° C. for overnight (16 h). The dropcasted coating did not appear clear at first, but become clear when theTHF evaporated.

PFPE/PDMS PU Coating Formulations and Properties

PFPE/PDMS PU are divided into two main categories based on the type ofpolymers used for the preparation of polyurethane films. Thesecategories include randomly grafted copolymer formulations and blockcopolymer formulations wherein one of the blocks is a random copolymerblock. These categories will be described in further detail below.

Randomly Grafted Copolymer Coating Formulations

Randomly grafted copolymers were obtained by grafting random copolymerswith PFPE or PDMS chains. This family of polymers can be further dividedinto sub-categories based on the composition of the grafted polymerchains or of the backbone chain of the random copolymer.

FPU Film Formation Example 1A(i), Example 1A(ii), Example 1A(iii),Example (iv)

These polymers are best described by the general formula:

where FS denotes PFPE, while R represents —OH groups. Meanwhile, M1denote styrene, and M2 denote all remaining components of P1. A broadrange of FPU films were prepared under different conditions usingExample 1A(i), Example 1A(ii), Example 1A(iii), Example 1A(iv), andExample 1A(v). The formulations and the performance of these films aresummarised in Table 7,

Examples 1A(i), 1A(ii), 1A(iii), 1A(iv), and 1A(v) were used to generatedurable amphiphobic films that were optically clear. The chemistry isshown in FIG. 7 and Scheme 7. Here, OH reacts with NCO groups togenerate urethane bonds and eventually a random network is formed calledpolyurethane.

The preparation of the film involved a very simple procedure that wasperformed at room temperature. All reagents were mixed and subsequentlydispensed onto glass slides. The samples were allowed to dry in the openair before thermal curing was performed at 120° C. For open air samplepreparation, humidity played an important role. Therefore, samplesprepared on highly humid days (>50%) were drop cast into an uncoveredcontainer, in order to minimize the accumulation of moisture.

PU Films Formation from P(TFEMA-HEMA)-g-PFPE 1B(i), 1B(ii), 1B(iii), and1B(iv).

Examples 1B(i), 1B(ii), 1B(iii), and 1B(iv) are represented by thefollowing general formula:[(FS)_(x)(R_(y)Mi_(100%-x-y))]_(n)where FS represents PFPE, R denotes 2-hydroxyethyl methacrylate groups,and Mi represents trifluoroethylmethyl methacrylate. These polymers wereprepared in various PFPE grafting density are described in Table 3. Thesynthesis was performed out according to the procedure described inScheme 3. This involves the synthesis of P(TFEMA-co-(HEMA-TMS) via ATRP,and the removal of the TMS group. During the subsequent step,PFPE-C(O)Cl was reacted with OH groups to provide Example 1B(i-iv).P(TFEMA-co-HEMA)-g-PFPE)] Example 1B(i-iv) based films were preparedunder different reaction conditions and their properties are summarizedin Table 8.

The above study involving Example 1B(i), Example 1B(ii), Example1B(iii), and Example 1B(iv) showed fascinating trends with respect tothe film properties. These properties involved the amphiphobicity, thedurability, and the optical properties of the films, and are describedin Example 11.

Preparation of PDMSPU Films using PDMS Graft Copolymers Example 1C

Polymers of this family are best described by general formula:

where FS represents PDMS, while R, M1 and M1 denote OH, Styrene, andMMA, respectively. These polymer were synthesized by the proceduredescribed in Example synthesis 1C(i), 1C(ii), 1C(iii), that involves thereaction of PDMS—C(O)Cl with P1.PDMSPU Film Formation by Drop Cast.

A representative synthesis of PDMSPU from grafted copolymers isdescribed here. HDID (11.9 mg, 0.055 mmol of NCO) and Example 1C(i) (5.0mg, 0.0064 mmol) were mixed together in 1.0 mL of acetone, and stirredat 65° C. for 60 min. This step was followed by the addition of P1solution (38.0 mg, 0.036 mmol) and allowed to react for another 150 min.The solution was cooled to RT and acetonitrile (1.6 mL) was added to thepolymer solution. The acetone was evaporated from via rotary evaporator.The solution in acetonitrile was diluted to 25 mg/mL as pureacetonitrile solution. The sample solution was drop casted and allowedfor 3-4 h at RT before thermal curing in a desiccator loaded with N₂inlet and outlet. The samples were annealed overnight at 120° C. beforeany characterization was performed.

Films based on the PDMS-bearing copolymers were prepared using differentamounts of the PDMS-bearing graft copolymers Examples 1C(i), 1C(ii), or1C(iii).

PDMSPU film formation on glass was challenging in THF, acetone and othercommon solvent, which are good for both PDMS and unmodified polyol.Therefore films were prepared in acetonitrile. The slippage phenomenawas due the hydrophobic PDMS and hydrophilic glass which does not likeeach other and thus, the coating solution always accumulated on lowerside of glass slide (downhill), as a result the prepared films wereneither uniform nor showing any good properties.

Acetonitrile was chosen for coating solutions drop casting because PDMSis insoluble in this solvent. Insoluble chain of PDMS forms core of themicelles having corona P1 chains outside. Thus upon drop casting themicelles solution of PDMS PU, PDMS does not come under immediate contactwith the glass and the slip phenomena disappears. Upon drop casting fromacetonitrile the films are initially not clear because of the micelleson the glass. But as the acetonitrile evaporates, PDMS chains started torelax in the absence of bad solvent (acetonitrile), and the filmsobtained clarity within 3-4 h at rt. Thermal curing of all samples wereperformed at 120° C. any PDMSPU film properties were examined.

Initially the optical clarity was poor because micellar solution. Theevaporation of acetonitrile helped the PDMS chains to relax (T_(g)=−125°C.), and hence the PDMS equal distribution throughout the film wasobtained. This helped not only to improve the optical clarity but alsothe amphiphobic properties of these films were enhanced by manytremendously.

PDMSPU Film Formation by Spin Coating.

A typical synthesis of PDMSPU from grafted copolymers is described here.HDID (10 mg, 0.047 mmol of NCO) and Example 1C(i) (10 mg, 0.021 mmol)were mixed together in 0.4 mL of THF and stirred at 60° C. for 30 min.This step was followed by the addition of P1 solution (21.0 mg, 0.0203mmol). The NCO/OH ratio employed for this synthesis was 1.27. Thereaction mixture was stirred for an additional 15 min at 90° C. beforethe sample was cooled to rt. Acetonitrile (1.6 mL) was added to thepolymer solution before spin coating treatment was performed. Drop castsamples were allowed to dry in the open air for ˜40 min until thesolvent had evaporated. The samples were annealed overnight at 120° C.before any characterization was performed. The formulations andconditions are shown in Table 9.

Film Formation from Example 1D (Acetylated-Grafted Polymer (without anyOH Reactive Group)

These polymers can be represented by the following general formula:[(FS)_(x)(R′_(y)Mi_((100%-x-y))]where FS represents PFPE or PDMS. Meanwhile, R′ denotes —OH groupedendcapped with C(O)CH₃, Mi represents S, MMA, MAA, BMA, IBMA, VE. Here,all of the OH groups were converted into C(O)CH₃. These polymers weretested for the performance of their resultant films after theend-capping of their reactive groups.FPU Film from Example 1D(i)

Polymer example 1D(i) (4.6 mg) was initially dissolved in THF (0.5 mL).To this solution was added P1 solution (10 mg, 0.0097 mmol) and NCO(2.20 mg, 0.0104 mmol). The final concentration of the copolymersolution was 27.5 mg/mL, while the NCO/OH ratio was 1.07. The solutionwas stirred at 60° C. for 1 h, and this solution was subsequently dropcast or spin-coated onto glass slides to prepare films. These films weresubsequently annealed for 16 h at 120° C. The properties of the filmsare shown in Table 11.

PDMS Based PU Films (Example 1D(ii))

Example 1D(ii) (2.9 mg) was initially dissolved in THE (0.5 mL). To thissolution was added P1 (12 mg, 0.012 mmol), and NCO (3.0 mg, 0.014 mmol),yielding a NCO/OH ratio of 1.21. The solution was stirred at 60° C. for1 h before it was cooled to room temperature and diluted withacetonitrile (2.0 mL). The final concentration of the copolymer solutionwas ˜7.2 mg/mL. The films were subsequently prepared via drop casting orspin coating and then annealed for 16 h at 120° C.

Various properties including water and oil-repellency, optical clarityand mechanical strength were evaluated for these end-capped FPU- andPDMSPU-based films and is shown in Table 12. In general the performanceis lower than the non-end capped FPU films/PDMSPU films. The mostsignificant property lost is the poor resistance to rubbing for thesefilms under 250 g weight rubbing for 800 cycles.

Film Formation from Example 2A and Example 2B

Preparation of FPU films from Example 2A

In order to prepare the FPU films, Example 2A (2.1 mg, 3.4 mmol of OH)was initially dissolved in THE (0.6 mL). To this solution was added P1solution (10 mg, 9.7 mol), and NCO (2.8 mg, 0.0132 mmol), providing aNCO/OH ratio of 1.3. The solution was stirred at 80° C. for 40 min. Thefilms were subsequently applied dropwise onto glass slides and annealedfor 16 h at 120° C. A list of mixing formulations is shown in Table 13.

The properties of the films obtained from PFPE-b-P(HEMA-S-MMA) aresummarized in Table 14, which clearly suggest that these films wereamphiphobic, as they could effectively repel both water and hexadecane.The durability of these films was lower than that of their random graftcopolymer-based counterparts, and changes observed after the rubbingtests were more pronounced. This deterioration was especially apparentin the case of film 5-B, which was prepared at a low NCO/OH ratio(1.01:1.0). However, the films prepared at a higher NCO/OH ratio(1.3/1.0, such as 5-A), were more stable than 5-B. Another problem withthese films was that they exhibited poor optical properties, withoptical transmittance values in the range between 40% T and 46% T. Insummary, these films exhibited poor performance than those prepared fromrandom graft copolymers.

Preparation of PDMSPU Films from Example 2B

In order to prepare the PDMS-based films, PDMS-b-P(HEMA-S-MMA) wasinitially dissolved in THE To this solution was added P1 solution andHDID in the ratios described in Table 15. The solution was subsequentlystirred at 60° C. for 2 h. The samples were diluted so that the finalsolvent composition was THF:AcN at a volume ratio of 1:4. The films weresubsequently prepared via drop casting or spin coating, and annealed for16 h at 120° C.

Example 5 Optical Clarity of the Herein-Described Amphiphobic ClearCoatings Prepared from Ingredients Made Under Approaches A and B

Optical Properties (% T).

Percent transmittance is a good measure of the optical clarity of films.In FIG. 5, the % T has been shown for various samples in the range of450-700 nm. Ordinary glass was taken as a reference with an opticaltransmittance of 98.8% T, while the optical transmittance of unmodifiedPU films was 97.7% T. The % transmittance were very high for both dropcasted and spin coated samples.

To study the influence of the fluorine content of the films on theiroptical properties, films were prepared from Example 1A(i). FIG. 2 showsthe changes in the transmittance at various fluorine compositions. Forthis purpose, the films were prepared using Example 1A(i) at same totalconcentration, and at same NCO/OH ratios. The % T measurements for thesesamples were observed in the range of 80.5% to 96.9%. As shown in theFIG. 2, the % T values increased as the Fluorine content was decreased.This trend indicates that lower fluorine content is useful for producingfilms with high optical clarity. See Tables 7, 8, 10, 11, 12, 13, and 16for results of optical clarity properties of the clear coatingsdescribed herein. FIG. 2 shows a plot of transmittance versus fluorinecontent. Notably, the optical clarity of certain clear coatings was veryclear. In particular, percentage transmittance values of approximately96% 97% were obtained for clear coats prepared using: Approach A ofExample 1A(i); Approach A of Example 1A(ii); and Approach A of Example1B(i) having a fluoro density of 13.6%.

The optical properties of the films prepared from the copolymers ofExamples 1C, 2A and 2B also showed good optical properties as shown inTable 10, Table 13, and Table 16, respectively.

Films having the lowest amount of grafted PFPE (Example 1B(i)) showedthe transmittance, which reached 94% for thick films of ˜400 nm. Incontrast, the transmittance drastically decreased among the films withhigher PFPE content, and films from Example 1B(iv) were almost opaque.

In general, the PDMSPU films exhibited good optical properties. Thefilms formed from Example 2B, PDMS-b-P(S-HEMA-MMA) exhibited opticaltransmittance values of 85.5% T (drop casted films) and 99.7% (spincoated) at a 10.1% PDMS grafting density.

Example 6 Durability of the Above-Described Amphiphobic Clear Coatings(Prepared from Ingredients Made Under Approaches A and B, Above)

The durability of these films was evaluated using a home-made rubbingdevice. The rubbing test was performed under 400 g weights at 40 rpm fordifferent intervals of time. The durability was examined based on thesliding angles properties before and after rubbing test. The results areshown in table 7, 8, 10, 11, 12, 13, and 16. In general films preparedfrom Example 1A(i) and Example 1A(i) were the most durable. The F orPDMS content affects the durability and films having more F % or PDMS %were found relatively less durable than having less F content as shownin table 7, 8, 10, 11, 12, 13, and 16.

To assess the effect of the NCO/OH ratio on the amphiphobic propertiesand the stability of the PFPE PU films, Example 1A(ii) based (16.5%PFPE) films were prepared at various NCO/OH ratios as shown in FIG. 3.All of the samples were prepared at rt via drop casting and thermalcuring at 120° C. for 12 h at a constant final concentration of 13.2mg/mL.

Sliding angle tests were performed to evaluate the influence of theNCO/OH ratio on the repellency against water and hexadecane. As theNCO/OH ratio was increased, the hexadecane sliding angles decreasedgradually. Meanwhile, the water sliding angles increased gradually asthe NCO/OH was elevated. At a NCO/OH ratio of 1.0, water had the lowestsliding angle while hexadecane has the highest sliding angle, of 26° and40°, respectively. As the NCO/OH ratio was increased, the water slidingangles increased further, and reached a maximum value of 58° at a ratioof 1.8. Meanwhile, hexadecane sliding angles continuously decreased andreached a final value of 32°. Apparently, the water sliding anglesincreased in a linear manner with increasing NCO/OH ratio. This trendmight be due to the presence of urethane groups formed after thereaction of OH and NCO.

All of these samples were subjected to a rubbing test for 40 min at 40rpm at a pressure of 5.8×10³ Pa. Hexadecane and water sliding angleswere measured both before and after the rubbing tests were performed. Asanticipated the water and hexadecane sliding angles decreased by littlemore for low NCO/OH ratio than for samples with higher NCO/OH content.For samples with NCO/OH ratios in the range of 1.1-1.4, the slidingangles remained almost unchanged after the rubbing tests.

Table 10 summarizes the durability of PDMS PU films. Drop casted filmsof several μm thickness were are were stable and showed little change insliding angles after rubbing for 2400 cycles at 250 g weight. Meanwhile,for spin coated films rubbing tests were performed for 60 min at 40 rpmusing a 100 g weight. One the other hand, the spin coated films showedsignificant decrease in their oil repellent changes after the durabilitytest.

The durability of the films was evaluated by measuring changes in thesliding angles of the films, as well as by changes to the structure ofthe film. As shown in Table 7, the durability of the films was highlydependent on the grafting densities of the PFPE chains. Polymers withlow grafting densities such as Example 1A(i) (13.6% PFPE), and Example1A(ii) (16.5% PFPE) exhibited much greater durability compared to thefilms prepared from Example 1A(iii), 1A(iv), or 1A(v). For example, thefilms generated from 1A(v) were the least stable and did not retaintheir structural integrity after they had been rubbed for 1 h with a 400g weight. Meanwhile, under the same rubbing test conditions, the filmsprepared from Example 1A(i) and Example 1A(ii) showed negligible changesin their hexadecane-repellent properties. Meanwhile, little change wasobserved in their water sliding angles.

The durability of the PDMSPU films prepared from coploymer of Example 2Bwas tested by via rubbing tests using a 250 g load at 40 rpm. Thesetests were conducted for 60 min. The films were durable and retainedtheir amphiphobic performance. This durability was particularlynoteworthy with respect to their hexadecane repellency.

Example 7 Anti-Fingerprint Properties of the Above-Described AmphiphobicClear Coatings Prepared from Ingredients Made Under Approaches A and B

The main purpose of this invention was to develop durable anti-fingerprint films. Human skin continuously secretes sweat, which is a complexmixture of many organic and inorganic materials. Deposition of sweat cancause screens to become fuzzy and unclear, which can interfere with theoperation of touchscreen devices. Therefore, the development of asolution to this problem is of key interest.

Therefore, our coated samples were tested for their anti-fingerprintproperties. For this purpose, an artificial finger print liquid wasinitially prepared by a standard method.⁵ Subsequently, a modifiedrubber stamp bearing circular patterns was used to imprint the films.The images of these imprints are shown in FIGS. 4a -d.

As shown in FIG. 4a , an artificial fingerprint was stamped ontoordinary glass. The circular pattern left by the stamp was clearlyvisible on the glass, indicating that the test liquid could easily betransferred onto the glass. Meanwhile FIG. 4b-c show impressions of thestamps left on PFPE PU films. It is very obvious that the test liquidshrank into tiny droplets on the film surfaces, suggesting that thesefilms exhibited strong anti-fingerprint properties. It was thus apparentthat the films shown in FIG. 4b-c had greater fingerprint-resistancethan the uncoated glass shown in FIG. 4a , Meanwhile, the film shown inFIG. 4d exhibited relatively poor fingerprint-resistance, which might bedue to the fact that the test liquid for finger print incorporated lowmolecular weight PDMS chains. The results suggest that films preparedfrom Examples 1A(i) and Examples 1A(ii) exhibited betterfingerprint-resistance.

Example 8 Anti-Ink Properties of the Above-Described Amphiphobic ClearCoatings Prepared from Ingredients Made Under Approaches A and B

Another interesting property of these PFPE PU and PDMS PU films is theirink-resistance. To evaluate the anti-ink properties of our films, apermanent marker was chosen to write on these films and the results areshown in FIG. 6. The unmodified PU film did not show any ink-resistance,as shown in FIG. 6a . Meanwhile, the films prepared from Example 1A(i)and Example 1B(i) were resistant against ink as shown in FIGS. 6b and 6c, respectively. Also, the faint lines of ink immediately shrank, asshown in FIGS. 6b and 6c . More interestingly, the coated films wereeasily cleaned and the ink could readily be wiped away. In contrast, itwas difficult to remove the ink from the ordinary glass or theunmodified PU films. Therefore, the PFPE PU films undoubtedly have greatpotential as anti-graffiti-resistant coatings.

Example 9 Ability of Clear Coatings to Allow Use of a Coated Touchscreenof an Electronic Device for the Above-Described Amphiphobic ClearCoatings Prepared from Ingredients Made Under Approaches A and B

Determination if Touch Screen Capability is Retained after Coating isApplied to Cellular Telephone

Example 1A(ii) (5.2 mg) was dissolved in 0.39 ml THF. To this solutionHDID (11.4 mg in 0.21 ml THF), and P1 (25 mg in 0.25 ml THF) were mixedtogether in 0.4 mL of THF. The samples solution was diluted with THFtill 18 mg/mL was obtained. The NCO/OH ratio employed for this synthesiswas 1.25. The solution was drop cast onto one part of a BLACKBERRY® cellphone screen. The films were allowed to cure at 38-40° C. for 12 h.

The purpose of this experiment was to test the touch screen features todetermine if a portion of the screen that was coated in an FPU coatingwas still able to be used to choose icon, and type on thescreen-displayed keyboard. Another portion of the touch screen was notcoated by FPU. For this purpose, modified PU films were produced at 5.3%fluorine content with ˜10 μm thickness. The coated and uncoated portionsof the touch screen were optically clear and indistinguishable from eachother. That is, both portions displayed equal optical clarity. Theentire touch screen, including the coated and uncoated portions,remained equally effective before and after coating. A keyboard wasdisplayed on the screen and letters were selected by touching thescreen. Letters were chosen from both the coated and uncoated portion.All of the touched letters were selected.

Anti-ink properties of the touch screen were tested with permanent inkmarker. Coated samples showed faint line that shrink immediately.Furthermore, the permanent marker's ink was easily cleaned up on thecoated portion. After wiping with a dry cloth it appeared completelyremoved from the screen. In contrast, the permanent marker marking onthe uncoated portion of the screen remained the same after wiping with adry cloth.

Anti-fingerprint properties of the touch screen were tested by applyinggreasy fingerprints. The coated portion of the touch screen, whichinitially showed greasy fingerprints, was easily cleaned by wiping witha dry cloth. After passing a dry cloth over it twice, there were noresidual fingerprints or streaks at all. The fingerprints appearedcompletely removed from the screen. In contrast, there were residualmarks on the uncoated portion of the screen after wiping with a drycloth 3 times. These residual marks made the uncoated portion of thescreen appear less optically clear (i.e., fuzzy).

These results suggest no disadvantages and significant advantages tocoating touch screens with the modified PU films described herein.

Example 10 Oil—and Water-Repellency of the Above-Described AmphiphobicClear Coatings (Prepared from Ingredients Made Under Approaches A and B,Above)

In general all of the films exhibited low water and hexadecane slidingangles. In addition, the test liquids left behind no residual marks ortraces of the liquid, which is a clear indication that these filmsexhibited strong amphiphobic properties. In general, water slidingangles for the densely PFPE/F grafted polymer Example 1A(v), (32% of OHreacted) were very low when they were tested against both water andhexadecane. These sliding angles were especially low in the case ofwater. The water and oil repellent sliding angles are shown in table SeeTables 7, 8, 10, 11, 12, 13, and 16.

The correlation between amphiphobicity vs. fluorine content wassystematically investigated. For this purpose, Example 1A(i) wasselected where the grafting density of PFPE was only 13.6%. Here, theNCO/OH ratio (1.25) and the final total concentration for all sampleswere kept at 20 mg/mL. The fluorine content was tuned by the addition ofP1. The effects of the film composition on the water and hexadecanesliding angles are summarized in FIG. 1.

We began at a higher fluorine content of 17.8 wt %, where waterexhibited lowest sliding angles (39.4°), while hexadecane showed 31.75.As the fluorine content was gradually decreased to 8.8 wt % the watersliding angles began to increase and reached 44.5° while hexadecanereached a very low sliding angle of 41.5°. A further decrease in thefluorine content from 8.8 to 3.8 wt % resulted in an increase in boththe hexadecane and water sliding angles and showed 54.7 for water and44.5 for hexadecane.

In general all of the films exhibited low water and hexadecane slidingangles. In addition, the test liquids left behind no residual marks ortraces of the liquid, which is a clear indication that these filmsexhibited strong amphiphobic properties. In general, water slidingangles for the densely PFPE/F grafted polymer example 1A(v), (32% of OHreacted) were very low when they were tested against both water andhexadecane. These sliding angles were especially low in the case ofwater.

To examine the amphiphobic properties of the films prepared from singlepolymer of this class, Example 1B(i) was used to prepare the FPU filmsat constant NCO/OH ratio (1.25). The sliding angles for water,hexadecane and diiodomethane are plotted FIG. 7c at various fluorinecontent ranging from 17.6 to 3.8 wt. % F. For all three test liquids, anincrease in F content decreased the sliding angles (enhancing theamphiphobic properties). The lowest sliding angles were obtained at themaximum F content where water, hexadecane and diiodomethane slides at39.4°, 31.7° and 27.5°, respectively.

The amphiphobicity of films prepared from copolymer of Example 2B weremeasured and are shown in Table 16. These films were prepared atdifferent PDMS grafting densities of 10.1% and 15.2%. Both of thesefilms exhibited low sliding angles when they were tested with water andhexadecane droplets. The hexadecane sliding angles were exceptionallylow for example, with hexadecane sliding angles of 7° and 10° observedfor films with PDMS grafting densities of 15.2% and 10.1%, respectively.Similarly, water sliding angles were very low as well for both spincoated and drop cast films. In general much better amphiphobicproperties were observed for these films in comparison with thoseexhibited by the grafted PDMSPU-based films.

Example 11 Scale-up of the Coating Process

Non-fluorinated Processing Solvents.

Embodiments of the present invention are advantageous becauseamphiphobic coatings were achieved without using fluorinated orsemi-fluorinated solvents for the preparation of the PFPE polyurethanefilms. That is, solvents such as THF or acetone can be used to readilyprepare these amphiphobic films.

Simplicity of the Method.

The coating process is also very simple and facile, as no stringentreaction conditions are required. The reagents are mixed at roomtemperature in the open atmosphere (at low humidity) without requiringany complex preparation conditions. Consequently, this method is veryeconomical.

Curing Conditions.

Currently, we are using 120° C. for at least 12 h as the curingprotocol. However, these conditions can be tuned to a lower temperature.

Example 12 Universal Coating Method

Example 1A(i) coating has been applied onto cotton, wooden piece andstainless steel disc by the following procedure.

Example 1A(i) (18.0 mg, 0.0310 mmol of OH) was dissolved in 2.0 mL ofTHF. To this solution was added (S_(x)-r-MMA_(y)-r-HEMA_(z))_(n) or P1(90 mg, 0.088 mmol of OH), diisocynate (31.2 mg, 0.146 mmol). The finalconcentration was raised to 138/3.5 ml (40 mg/ml), while NCO/OH was1.24.

Cotton coating.

Cotton swatches (2 pieces) were dipped into 1.0 mL of the above solutionfor 20 min at RT. The soaked cotton samples were taken out and allow toair dry for 20 min before curing at 120° C. overnight.

Metal coating. 0.2 mL of the above solution was drop cast onto stainlesssteel disc (3.14 cm²). The sample was allowed to dry in a desiccator for25 min, before curing the sample in oven at 120° C. for overnight priorto any property test.

Wood-piece coating. 2.0 ml of the above coating solution wasaero-sprayed on wooden strip (1.4″×1.2″ inches²) using as home-madeaero-spraying instrument. The sample was cured overnight before anymeasurements properties were tested.

Water and diiodomethane slides on cotton, cotton, wooden piece andstainless steel disc. Meanwhile, wooden piece and stainless steel discalso repels hexadecane, as shown in FIG. 9. In another study, Example1C(i) was used to coated cotton, wooden piece and stainless steel disc.All these samples after coating repel water, while stainless steel repelhexadecane as well.All these indicates the current clear technology is applicable to manysolid substrates and thus enhances many the scope of its applications.

Example 13 Effect NCO/OH Ratio on Durability of the Films

To assess the effect of the NCO/OH ratio on the amphiphobic propertiesand the stability of the PFPE PU films, Example 1A(ii) based (16.5%PFPE) films were prepared at various NCO/OH ratios as shown in FIG. 3.All of the samples were prepared at rt via drop casting and thermalcuring at 120° C. for 12 h at a constant final concentration of 13.2mg/mL.

Sliding angle tests were performed to evaluate the influence of theNCO/OH ratio on the repellency against water and hexadecane. As theNCO/OH ratio was increased, the hexadecane sliding angles decreasedgradually. Meanwhile, the water sliding angles increased gradually asthe NCO/OH was elevated. At a NCO/OH ratio of 1.0, water had the lowestsliding angle while hexadecane has the highest sliding angle, of 26° and40°, respectively. As the NCO/OH ratio was increased, the water slidingangles increased further, and reached a maximum value of 58° at a ratioof 1.8. Meanwhile, hexadecane sliding angles continuously decreased andreached a final value of 32°. Apparently, the water sliding anglesincreased in a linear manner with increasing NCO/OH ratio. This trendmight be due to the presence of urethane groups formed after thereaction of OH and NCO.

All of these samples were subjected to a rubbing test for 40 min at 40rpm. Hexadecane and water sliding angles were measured both before andafter the rubbing tests were performed. As anticipated the water andhexadecane sliding angles decreased by little more for low NCO/OH ratiothan for samples with higher NCO/OH content. For samples with NCO/OHratios in the range of 1.1-1.4, the sliding angles remained almostunchanged after the rubbing tests.

Example 14 Amphiphobicity

Polymers with lower PFPE grafting density are displayed loweramphiphobic properties than film with higher PFPE grafting. All polymersExample 1B(i), Example 1B(ii), Example 1B(iii), and Example 1B(iv)displayed low hexadecane (oil) sliding angles, while, water slidingangles for the highest grafted polymer Example 1B(iv), 32% of OHreacted, were best.

To examine the amphiphobic properties of the films prepared from singlepolymer of this class, Example 1B(i) was used to prepare the FPU filmsat constant NCO/OH ratio (1.15). The final concentration of the polymersolution was 20 mg/ml. The wt. % of PFPE or F % content was graduallyvaried. We began at highest Fluorine content of 17.6 wt %. At thiscomposition, water has lowest sliding angles (34°), while hexadecane has48° among the samples. By decreasing PFPE content, the water slidingangles started to increase, while for hexadecane it first decreased andthen started to increase. Hexadecane sliding angles started again toincrease once they reached their minimum 37.5° at 6.1 wt. % of PFPE. Interms of fluorine content, the best properties for hexadecane wereobtained at 3.8 wt % of fluorine.

Amphiphobicity of Example 1C(i)-Based Films.

Films obtained by drop casting and spin coating from this family ofpolymers were evaluated via water and hexadecane sliding anglemeasurements. As shown in Table 10, all of the polymers provided filmsthat exhibited low water sliding angles. Low hexadecane sliding angleswere also observed for films prepared from Example 1C(i), where the PDMSgrafting density was only 11.3%. As shown in FIG. 8, sliding angles forPDMSPU films prepared from Example 1C(i) by drop casting, where thehexadecane sliding angles are as low as 3° (5 μL) while water slides at40° (15 μL).

Example 15 Embedding of Silica Particles in Durable Amphiphobic ClearCoating

Two types of silica particles were used to embed silica particles inamphiphobic clear coatings. One was an unmodified silica particle (size˜400 nm), and the other was a bifunctional silica particle (bearingamine and fluorine on the surface, size ˜100 nm). These particles wereincorporated into an FPU matrix consisting of NCO (5.0 mg), P1 (10 mg)and Example 1A (i) (5.0 mg) in the ratio shown in Table 17. First, thesilica particles were partially dispersed into THF. This was followed bythe addition of a THF solution of FPU into the partially dispersedsilica particles. In the cases of samples 3 and 4, a TFT:THF (30:70,v/v) solvent mixture was used to disperse the coated silica particlesinto the matrix. The films were drop cast onto glass slides and thesolvent was allowed to evaporate at room temperature. After 20 min, thesamples were cured at 120° C. for 12 h before any performance tests wereperformed.

Silica particles (both coated and uncoated) were successfullyincorporated into FPU films, as shown in Table 17. FPU filmsincorporating silica particles films retained their amphiphobicproperties even at higher particle loadings reaching 1.5 times theoriginal mass of the FPU matrices. However, at very high particleloadings (more than double the mass of the original FPU matrix), thewater contact angles increased to 121°. However, the durability of thefilms decreased when greater amounts of silica particles wereincorporated into the system.

Example 16 PFPE Grafted Polyol

To prepare PFPE grafted polyol, either PFPE-bearing methacrylates orPFPE-bearing acrylates are mixed in the presence of one or a combinationof monomers. Suitable monomers include acrylates, hydroxyl-bearingacrylates, styrenes, methacrylates, hydroxyl-bearing methacrylates,and/or vinyl esters. The acrylate and monomer(s) are mixed in a flasksuitable for free radical polymerization either in bulk or in thepresence of a solvent such as tetrahydrofuran or a mixture oftetrahydrofuran and trifluorotoluene to form a reaction mixture. Thisreaction mixture is stirred using either a mechanical or a magnetic stirbar. Optionally, a chain transfer catalyst or chain transfer agent isadded to the reaction mixture to control molecular weight. At thisstage, the flask is loaded with AIBN (or any similar initiator) andpolymerization begins upon exposure to light and/or heat, depending onthe type of initiator. Once the polymerization reaches a desired degreeof monomer conversion, the reaction is stopped. The solid polymerproduct is collected by its precipitation in a poorly solvating solventor by evaporation of a solvent.

Example 17 Polysiloxane Grafted Polyol

To prepare polysiloxane grafted polyol, either polysiloxane-bearingmethacrylates or siloxane acrylates are mixed in the presence of one ora combination of monomers. Suitable monomers include acrylates,hydroxyl-bearing acrylates, styrenes, methacrylates, hydroxyl-bearingmethacrylates, and/or vinyl ester. The siloxane methacrylates orsiloxane acrylates (e.g., PDMS acrylate) and monomer(s) are mixed in aflask suitable for free radical polymerization either in bulk or in thepresence of a solvent to form a reaction mixture. The reaction mixtureis stirred using either a mechanical or a magnetic stir bar. Optionally,a chain transfer catalyst or reagent is added to the reaction mixture tocontrol molecular weight. At this stage, the flask is loaded with AIBN(or any initiator) and polymerization will begins upon exposure to lightand/or heat, depending on the type of initiator. Once the polymerizationreaches to a desire degree of monomer conversion, the reaction isstopped. The solid polymer product is collected by its precipitation ina poorly solvating solvent or by evaporation of a solvent.

Example 18 Preparation of Water-Based PDMS PU Film

Individually, the following three ingredients were dissolved in aminimum amount of acetone, and then the three solutions were combined inany order. Unmodified polyol P1-0 Purchased from Sherwin-Williams) (72mg, 0.08 mmol of OH) was dissolved in acetone (1 mL).PDMS-modified-polyol (see Example 1C(v)) (20 mg at 6.1% graftingdensity, 0.017 mmol of OH) was dissolved in acetone (1.0 mL). DesmodurBL 3272 MPA (available from Bayer, see structure below) (50 mg, 0.12mmol of NCO) was dissolved in acetone (1.0 mL). Desmodur BL 3272 MPA isa blocked (meaning protecting groups are present) AliphaticPolyisocyanate based on hexamethylene diisocyanate and dissolved inpropylene glycol monomethyl ether acetate). Once mixed together,distilled water (5.0 mL) was added to the resultant mixture. The volumewas then reduced in vacuo using a rotary evaporator (Büchi) so that theacetone was substantially removed and the water remained. The resultantwhite emulsion-like solution was termed “coating solution”.

The coating solution was drop cast onto a glass slide using a pipette,and the slide was held flat and was placed in a desiccator. Thedessicator had pressurized air flowing through it via an inlet and anoutlet. The coated slide was allowed to evaporate in the dessicator withthe air flow for 4 h at room temperature. At this point, the uncuredcoating's appearance was not transparent. The coated slides were thenheated so that the coating could cure for 12 h at 150° C. After heating,the coating's appearance was transparent. In tests for amphiphobicproperties of coatings prepared in this manner, cured coatings haddroplets of both water and hexadecane slide off the coated surface. Theslide angles for these coatings was approximately 5° for hexadecane, andapproximately 45° for water. By comparison, uncoated slides appear wetand have no sliding droplets at any angle. Films prepared in this wayshowed optical transmittance of approximately 96%, which indicated highoptical clarity.

Example 19 Preparation of PDMS PU Film from Example 1C(iv) in Dimethylcarbonate

Example 1C (iv) (3.0 mg, 0.006 mmol) was dissolved in acetone (1.0 mL).HDID (8.8 mg, 0.053 mmol of NCO) was added to the above solution, andthe combined mixture was heated and stirred at 65° C. for 60 min. P1-0(19.0 mg, 0.0418 mmol) was added to the mixture and stirring and heatingwere continued at 65° C. for an additional 150 min. The mixture wascooled to room temperature and dimethyl carbonate was added (3.0 mL).The mixture's volume was reduced by removing acetone, dimethyl carbonateand other volatile solvents in vacuo via a rotary evaporator. Theresultant concentrated solution was adjusted to 15 mg/mL in dimethylcarbonate (DMC). This coating solution was dispensed onto glass slidesand the DMC was allowed to evaporate for ˜2 h at room temperature in adesiccator under an active N₂ atmosphere. The coated glass slides werethermally cured in an oven at 120° C. overnight. The PDMS PU filmobtained was optically clear (97.4±0.1), and oil- and water-repellent.Also the film possess anti-ink properties.

Example 20 Preparation of PDMS PU Film from Example 1C(iv) in Acetone

Example 1C (iv) (3.0 mg, 0.006 mmol) was dissolved in acetone (1.0 mL).HDID (8.8 mg, 0.053 mmol of NCO) was added to the above solution, andsample was heated and stirred at 65° C. for 60 min. P1-0 (19.0 mg,0.0418 mmol) was added to the above reaction mixture and continuedstirring at 65° C. for an additional 150 min. The solution was cooled toroom temperature the final concentration was adjusted to 15 mg/mL inacetone. This coating solution was dispensed onto glass slides andallowed the acetone to evaporate for ˜1 h in a desiccator with N₂ inletand outlet. The coated glass slides were thermally cured at 120° C.overnight. The PDMS PU film obtained was optically clear (94.8±3.5) andoil- and water-repellent.

Example 21 Preparation of PDMS PU Films without Preheating BeforeCasting

Example 1C (iv) (6.25 mg, 0.012 mmol of OH in 0.5 mL acetone), HDID (4.4mg, 0.026 mmol of NCO in 0.10 mL acetone), and P1-0 (4.75 mg, 0.010 mmolof OH in 0.1 mL of acetone) were mixed together in any order. To thissolution, was added acetonitrile (1.0 mL). Notably, this mixture was notheated. All acetone and about half of acetonitrile were removed undervacuum using a rotary evaporator till the volume of solution was reducedto ˜0.5 mL. Fresh acetonitrile (0.35 mL) was added to dilute the coatingsolution to 15 mg/mL. This coating solution was dispensed onto glassslides using a pipette. The slides were placed in a desiccator, havingan N₂ atmosphere gently freshened through an inlet and out-let, forapproximately 3 h. The acetonitrile evaporated. The coated slides werethen thermally curried in an oven overnight in an oven at 120° C. Thefilms obtained were optically clear (98.9±0.1), oil- andwater-repellent, and ink-resistant.

Example 22 Preparation of P(S-alt-MA)-g-PDMS

Commercially available Poly(styrene-alt-maleic anhydride) (P(S-alt-MA),average Mn ˜1,700 by GPC, and maleic anhydride (˜32 wt %) were placedunder vacuum at 60° C. for 4 hours to remove any volatile residual.Poly(styrene-alt-maleic anhydride) (0.8 g), PDMS monohydroxy terminated(2.0 g), THF (˜10.0 mL), and pyridine (˜1.0 mL) were charged into areactor. The resulting mixture was heated to and maintained at 60° C.for 48 hours. Solvents were then removed under vacuum at 60° C. for 4hours, and viscous Poly(styrene-alt-maleic anhydride)-g-PDMS(P(S-alt-MA)-g-PDMS) was obtained.

Example 23 Preparation of PDMS-b-PGMA

Bromide terminated PDMS was prepare through published method (J. Mater.Chem. A, (2014), 2:8094-8102). Bromide-terminated PDMS (2.0 g),copper(I) bromide (0.060 g), copper(II) bromide (0.010 g), acetone (5.0mL), and N,N,N′,N′,N″-pentamethyldiethylenetriamine (70 μL) were chargedinto a nitrogen filled reactor, and the mixture was degassed throughthree freeze-pump-thaw cycles. Then degassed glycidyl methacrylate (1.8mL) was added into the reactor. The reactor was heated to 55° C. for 3hours. Then a crude product was poured into methanol (50 mL) andPDMS-b-PGMA precipitated, Crude PDMS-b-PGMA solid was re-dissolved inacetone (10 mL) and precipitated in methanol (50 mL) again. Thisprecipitation process was repeated three times until a blue color wasremoved and purified PDMS-b-PGMA product was obtained. This productPDMS-b-PGMA was placed under vacuum for 4 hours to remove any residualsolvents.

Example 24 Preparation of PEI-g-PDMS, where Mn of PEI ˜10,000 (“P20-1”)

Commercially available branched polyethylenimine (PEI branched, averageMw ˜25,000 by LS, average Mn ˜10,000 by GPC) was placed under reducedpressure at 60° C. for 24 hours to remove any volatiles. PEI branched(2.0 g) and PDMS monoglycidyl ether (1.0 g), chloroform (˜10.0 mL),triethylamine (˜2.0 mL) were charged in a reactor. (In subsequentstudies, a 1:1 mass ratio of PEI and PDMS monoglycidyl ether were used,and the synthesis was also successful.) PEI branched (2.0 g) and PDMSmonoglycidyl ether (1.0 g), chloroform (˜10.0 mL), triethylamine (˜2.0mL) were charged in a reactor. The resulting mixture was heated to 60°C. and maintained for 48 hours. After that, chloroform and triethylaminewere removed under reduced pressure at 60° C. for 4 hours, and a waxyproduct (“P20-1”) was obtained. See FIG. 11 for structural formulae ofP20-1 and P20-2.

Example 25 Preparation of PEI-g-PDMS, where Mn of PEI Mn ˜1800 (“P20-2”)

The commercially available branched polyethylenimine (PEI branched,average Mw ˜2000 by LS (light scattering), average Mn ˜1800 by GPC, 50wt. % in H₂O) placed under reduced pressure using vacuum at 60° C. for24 hours to remove the volatile residual. If precipitate was observed,it was removed by centrifugation; if not, it was used as is. Drybranched PEI (1.0 g) and PDMS monoglycidyl ether (2.0 g), chloroform(˜10.0 mL), triethylamine (˜2.0 mL) were charged into a reactor whichwas under N₂. The mixture was heated to 60° C. and kept for 48 hours.

In initial syntheses, chloroform and triethylamine were removed invacuum at 60° C. for 4 hours, and viscos P20-2 was left.

In further syntheses, the reaction mixture was condensed to half of itsinitial volume under vacuum, and its temperature was increased to 63° C.After another 24 hours, chloroform was removed under vacuum at 60° C.for 4 hours, and viscous PEI-g-PDMS was obtained.

Example 26 Preparation of PDMS-b-Polyamine (“P20-3”)

Poly(dimethylsiloxane)-block-poly(2-hydroxyethyl acrylate) (PDMS-b-PHEA)was prepared using a published method (Liu G., et al. J. Mater. Chem. A,2014, 2, 8094). PDMS₆₀-b-HEA₂₀ (1.0 g), carbobenzyloxyglycine (0.300 g),1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide (0.400 g), THF (10 mL) andtriethylamine (2.0 mL) were charged into a reactor. The mixture washeated to 60° C. and kept for 24 hours. After that, the crude reactionmixture was precipitated in water. The resultant waxy polymer wasdissolved in ˜5 mL trifluoroacetic acid and heated to 70° C. for 2hours. Then trifluoroacetic acid was removed by vacuum and the waxyresidue was dissolved in 5 mL of triethylamine and precipitated inexcess amount of water. See FIG. 12 for structural formulae of P20-3.

Example 27 Preparation of Polyacrylic Acid-g-PDMS (“P20-4”)

Acrylic acid (1.4 mL), methyl methacrylate (19.7 mL),azobisisobutyronitrile (AIBN, 2.5 g), acetone (300 mL) was charged intoa reactor. The mixture was heated to 55° C. and kept for 24 hours. Thenthe reaction was condensed to ˜100 mL by vacuum and precipitated in ˜400mL hexanes. The solid precipitate is poly(acrylic acid-co-methylmethacrylate) (P(AA-co-MMA)) and was dried by vacuum. To prepare P20-4,P(AA-co-MMA) (1.0 g), PDMS monoglycidyl ether (1.0 g), chloroform (˜10.0mL), pyridine (˜0.5 mL) were charged into a reactor. The mixture washeated to 60° C. and kept for 48 hours. After that, solvents wereremoved under vacuum at 60° C. for 4 hours, and waxy P20-4 was left. SeeFIG. 13 for structural formulae of P20-4.

Example 28 Preparation of a (Polyanhydride and PolycarboxylicAcid)-g-PDMS (“P20-5”)

A commercially available poly(styrene-co-maleic anhydride) (average Mn˜1,700 by GPC, maleic anhydride ˜32 wt %) was vacuumed at 60° C. for 4hours to remove the volatile residual. Poly(styrene-co-maleic anhydride)(0.8 g), PDMS monohydroxy terminated (2.0 g), THF (˜10.0 mL), pyridine(˜1.0 mL) were charged into a reactor. The mixture was heated to 60° C.and maintained for 48 hours. After that, solvents were removed undervacuum at 60° C. for 4 hours, and viscous P20-5 was left. See FIG. 14for structural formulae of P20-5.

Example 29 Preparation of Another (Polyanhydride and PolycarboxylicAcid)-g-PDMS (“P20-6”)

The commercially available poly(styrene-co-maleic anhydride) (average Mn˜1,700 by GPC, maleic anhydride −32 wt %) was vacuumed at 60° C. for 4hours to remove the volatile residual. Poly(styrene-co-maleic anhydride)(0.4 g), PDMS monoglycidyl ether (1.0 g), THF (˜10.0 mL), pyridine (˜1.0mL) were charged into a reactor. The mixture was heated to 60° C. andmaintained for 48 hours. After that, solvents were removed under vacuumat 60° C. for 4 hours, and viscous P20-6 was left. See FIG. 15 forstructural formula of P20-6.

Example 30 Preparation of Polyol-g-PDMS (“P20-7”), Wherein the Polyolwas Poly(HEMA-co-St-co-BMA-co-MMA)

2-Hydroxyethyl methacrylate (HEMA, 6.0 mL), styrene (St, 5.0 mL), butylmethacrylate (BMA, 5.0 mL), methyl methacrylate (MMA, 5.0 mL),azobisisobutyronitrile (AIBN, 1.0 g), THF (100 mL) was charged into areactor. The mixture was heated to 70° C. and maintained for 12 hours.Then the reaction was precipitated in ˜400 mL hexanes. The solidprecipitate is Poly(HEMA-co-St-co-BMA-co-MMA) and was dried by vacuum.PDMS monohydroxy terminated (2.0 g) and oxalyl dichloride (1.6 g) wascharged into a reactor. After 12 hours of reaction at room temperature,excess oxalyl dichloride was removed by vacuum at 40° C. for 4 hours.The residue liquid was PDMS end functionized by acid chloride group(PDMS-COCl). The freshly prepared PDMS-COCl (0.3 g) was added dropwiseinto a mixture of poly(HEMA-co-St-co-BMA-co-MMA) (1.0 g), THF (10 mL)and triethylamine (1 mL) in a reactor and reacted for 24 hours. Then thecrude reaction mixture was added into 100 mL water, and the polymerprecipitate was collected was dried under vacuum. See FIG. 16 forstructural formula of P20-7.

Example 31 Preparation of PEI-g-PFPO (“P20-8”)

The commercially available branched polyethylenimine (PEI branched,average Mw ˜25,000 by LS, average Mn ˜10,000 by GPC) was placed underreduced pressure at 60° C. for 24 hours to remove the volatile residual.PEI branched (4.0 g) and PFPO bearing one terminal carboxyl group(PFPO—COOH, with a trade name Krytox 157 FSL) monoglycidyl ether (2.0g), chloroform (˜10.0 mL), trifluorotoluene (˜5.0 mL), andmethoxyperfluorobutane (˜3.0 mL) were charged into a reactor. Themixture was heated to 60° C., then 2-chloro-1-methylpyridinium (CMPI,0.50 g) iodide was added, and the 60° C. temperature was maintained 24hours. After that, the solution was separated from any insolublematerial (e.g., reacted coupling agent), and the solvent were removedunder vacuum at 60° C. for 4 hours. Waxy P20-8 product was obtained. SeeFIG. 17 for structural formula of P20-8.

Example 32 Preparation of P(S-alt-MA)-g-PEO₇₅₀

In preliminary studies, P(S-alt-MA)-g-PEO₇₅₀ was prepared using thefollowing procedure. This synthesis has not been optimized. Commerciallyavailable Poly(styrene-alt-maleic anhydride) (P(Sty-alt-MA), average Mn˜1,700 g/mol by GPC, maleic anhydride ˜32 wt %) and Poly (ethyleneglycol) methyl ether (PEO₇₅₀₋OH, average Mn=750 g/mol) were placed underreduced pressure at 60° C. for 4 hours to remove any volatile residuals.Poly(styrene-alt-maleic anhydride) (2.0 g), PEO₇₅₀-OH (1.4 g), anhydrousTHF (˜20.0 mL), pyridine (˜1.0 mL) were charged into a reactor to form amixture. The mixture was heated to and maintained at 60° C. for 24hours. Approximately half of the volume of the mixture was removed byvacuum, and the temperature was increased to 80° C. and maintained foranother 24 hours. Solvents were then removed under vacuum at 60° C. for4 hours. The remaining product was Poly(styrene-alt-maleicanhydride)-g-PEO₇₅₀ (P(S-alt-MA)-g-PEO₇₅₀).

Example 33 Preparation of P(S-alt-MA)-g-PEO₂₀₀₀

In preliminary studies, P(S-alt-MA)-g-PEO₂₀₀₀ was prepared using thefollowing procedure. This synthesis has not been optimized. Commerciallyavailable Poly(styrene-alt-maleic anhydride) (“P(S-alt-MA”) was driedunder vacuum at 60° C. for four hours prior to use. (This copolymer hada weight percentage of maleic anhydride of −32 wt %.) Commerciallyavailable poly (ethylene glycol) methyl ether (“PEO₂₀₀₀₋OH”) was alsodried prior to use under vacuum at room temperature for 4 hours. (Theaverage molecular weight of the poly (ethylene glycol) methyl ether wasMn=2000 g/mol).

Poly(styrene-alt-maleic anhydride) (2.0 g), PEO₂₀₀₀-OH (2.0 g),anhydrous THF (˜20.0 mL), pyridine (˜1.0 mL) were charged into a reactorto form a mixture. The mixture was heated to 60° C. and kept for 24hours. Then, around half of the volume was removed by vacuum, and thetemperature was increased to 80° C. and kept for another 24 hours. Afterthat, solvents were removed in vacuum at 60° C. for 4 hours, and theremaining product was Poly(styrene-alt-maleic anhydride)-g-PEO₂₀₀₀(P(S-alt-MA)-g-PEO₂₀₀₀).

Example 34 Preparation of P(S-alt-MA)-g-PEO₅₀₀₀

In preliminary studies, P(S-alt-MA)-g-PEO₅₀₀₀ was prepared using thefollowing procedure. This synthesis has not been optimized. The averageMn of P(S-alt-MA was ˜1,700 as determined by GPC.

Commercially available poly(styrene-alt-maleic anhydride) was driedunder vacuum at 60° C. for four hours prior to use. (This copolymer hada weight percentage of maleic anhydride of ˜32 wt %.) Commerciallyavailable poly (ethylene glycol) methyl ether was also dried prior touse under vacuum at room temperature for 4 hours. (The average molecularweight of the poly (ethylene glycol) methyl ether (“PEO₅₀₀₀-OH”) wasMn=5000 g/mol.)

The following components were charged into a reactor to form a mixture:

-   -   (i) Poly(styrene-alt-maleic anhydride) (0.8 g),    -   (ii) PEO₅₀₀₀-OH (2.0 g),    -   (iii) anhydrous THF (˜20.0 mL), and    -   (iv) pyridine (˜1.0 mL).

The mixture was heated to and maintained at 60° C. for 24 hours. Then,around half of the volume was removed by vacuum, and the temperature wasincreased to 80° C. and maintained for another 24 hours. Solvents werethen removed in vacuum at 60° C. for 4 hours, and the remaining productwas Poly(styrene-alt-maleic anhydride)-g-PEO₂₀₀₀(P(S-alt-MA)-g-PEO₂₀₀₀).

Example 35 Preparation of Polyol-g-PIB

In preliminary studies, Polyol-g-PIB was prepared using the followingprocedure. This preparation has not been optimized. Commerciallyavailable hydroxyl terminated polyisobutylene (PIB-OH, 0.20 g) wasdissolved in ˜5 mL anhydrous THF, and 1.0 mL oxalyl chloride was addedinto the solution all at once. After 12 hours of reaction at roomtemperature, PIB-OH had converted into acid chloride terminatedpolyisobutylene (PIB-COCl). Solvent and excess amount of oxalyl chloridewere then removed by vacuum at 60° C. for 4 hours. PIB-COCl wasre-dissolved in ˜2 mL anhydrous THF, and the solution was added intopolyol (0.10 g) in anhydrous THF (˜3 mL) solution. After 24 hours ofreaction at room temperature, solvent was removed in vacuum at 60° C.for 4 hours, and Polyol-g-Polyisobutylene (Polyol-alt-PIB) was left.

Example 36 Preparation of Polyol-g-PB

Polybutadiene-g-polyol was prepared by reacting dicarboxyl-terminatedpolybutadiene (“CTPB”) with oxalyl chloride, followed by esterificationwith methanol and polyol in sequence.

Specifically, dicarboxyl-terminated PB (0.30 g), oxalyl chloride (70 μL)and dichloromethane (3.0 mL) were mixed in a glass flask under N₂atmosphere at room temperature. The reaction of aforementioned mixturewas allowed to vigorously stir for 12 h.

The mole ratio of the (COCl)₂ to CTPB was approximately 10˜13. Themixture's volume was reduced to remove the residual oxalyl chloride, andacid chloride-terminated PB was obtained as a yellow liquid. Methanol(4.5 μL) was added to the flask and the contents was stirred under N₂atmosphere at room temperature for 12 h. After reaction, one end of a PBchain was terminated by ester and the other end was acid chloride. Themole ratio of the MeOH to acid chloride-terminated polybutadiene wasapproximately 1.1-1.3.

Subsequently, the obtained PB with one end terminated with acid chloridewas added into a CH₂Cl₂ (6 mL) solution of polyol (0.15 g) dropwise.This mixture was stirred under N₂ atmosphere at room temperature for 24h. The mole ratio of the ester-terminated polybutadiene to polyol wasapproximately 1.1˜1.3. The resulting polybutadiene-g-polyol product wasa yellow viscous liquid. Coatings of polybutadiene-g-polyol modifiedpolyurethane are described in Example 43.

Example 37 Preparation of polyepoxide-g-PDMS (“P30-1”)

A resin that had more than one glycidyl group, eg. Bis-A (0.10 mL,containing 0.68 mmol glycidyl groups) was mixed with an amount of aparticular P20 (types of P20 and amounts are listed in Table 19) inchloroform (0.50 mL). The mixture was heated to 60° C. and thetemperature was maintained for 1 hour. These samples were used in thenext step (Step 3 of FIG. 10) without any further purification.

Example 38 Preparation of PFPO Containing Glycidyl Anchor, Also Known asPolyepoxide-g-PFPO (“P30-2”)

A resin contains more than one glycidyl groups, eg. Bis-A (0.10 mL,containing 0.68 mmol glycidyl groups) was mixed with P20-8 inchloroform/trifluorotoluene/methoxyperfluorobutane (0.50 mL, 10/5/3v/v/v). The mixture was heated to 40° C. and kept for 1 hour. Thesesamples were used in the next step (Step 3 of FIG. 10) without anyfurther purification.

Example 39A Preparation of PDMS Micellar Solutions (Step 3 of FIG. 10)Wherein Hardener was Mixed with P30

Activator (0.10 mL, contains nonylphenol/triethanolamine/piperazinepolyoxypropylenediamine=1/0.0621/0.0200/0.583=m/m/m/m) was mixed intoany of the P30 polymer mixture samples. After that, dimethyl carbonate(DMC, ˜2 mL) and dimethylformamide (DMF, ˜0.1 mL) were added into themixture. A clear solution with slightly bluish tint formed, which wasthe uncured epoxy resin solution ready for coating in the Example 40.

Example 39B Preparation of PDMS Micellar Solutions (Step 3 of FIG. 10)Wherein Bis-A was Mixed with P20 and Hardener

Two procedures were used to cure epoxy coatings. In the first procedure,only PEI-g-PDMS (or another P20) was used to cure epoxy coatings. Thatis, no other hardener was added. In the second procedure, PEI-g-PDMS (oranother P20) and an additional hardener were used to cure epoxycoatings. Hardener includes nonylphenol/triethanolamine/piperazinepolyoxypropylenediamine=1/0.0621/0.0200/0.583=m/m/m/m.

Using the first procedure, Bis-A (0.10 mL) and PEI-g-PDMS (20 mg) weredissolved in butanone (2.0 mL) to form a mixture. DMF (0.2 mL) was addedinto the mixture. Using the second procedure, Bis-A (0.10 mL),PEI-g-PDMS (20 mg) and a hardener (30 mg) were dissolved in butanone(2.0 mL) to form a mixture. DMF (0.2 mL) was added into the mixture.Uncured epoxy-based resin solutions were ready for coating.

Example 40 Epoxy Coating Procedure and Curing

Different thickness of coat could be achieved by casting differentamount of solution from Step 3. For example, 0.20 mL of solution fromExample 39A was cast on ⅔ area of a 1′×3′ glass plate, and that gave a˜7 um thick coating. The glass plate was put on a horizontal bench, andthe solution was evenly casted on the glass plate. Around 20 min wereallowed to pass for most of the solvent to evaporate. To fully evaporatethe solvent(s), the coated glass plate was then placed into a dryingcabinet with a dust-removed air purging system for more than 1 hour.

The coated epoxy resin films were cured at room temperature or underheating. At room temperature in the drying cabinet, the films weresolidified after 8 hours, and were fully cured after ˜72 hours. At 120°C. in a heating oven, films were fully cured in 1 hour, After fullycuring, the PDMS modified epoxy resin coating on the substrate wasglossy and clear. When tilting the coated glass plate, hexadecane (˜0.02mL) and water (˜0.05 mL) droplets rolled off the coated area. Thecoating was strong enough to resist scratches by fingernails.

Example 41 Preparation of PEO Modified Polyurethane Coating UsingP(S-alt-MA)-g-PEO_(750/2000/5000)

In preliminary studies, PEO Modified Polyurethane Coating UsingP(S-alt-MA)-g-PEO_(750/2000/5000) were prepared using the followingprocedure. This preparation has not been optimized. To obtainPEO-modified polyurethane coatings the following three components (i,and iii) were dissolved in butanone (2.0 mL) and DMF (0.5 mL):

-   -   (i) P(S-alt-MA)-g-PEO (20 mg) having three different PEO        (differing by molecular weight) as described in the previous        Examples;    -   (ii) a poly(hexamethylene diisocyanate) (predominantly trimer,        65 mg, 80 wt % in butyl acetate, such as those sold under the        trademarks UH80-ULTRA SYSTEM® by SHERWIN-WILLIAMS Co.); and    -   (iii) polyol (100 mg, containing 32 wt % HEMA).

Different thicknesses of coatings could be achieved by casting differentamounts of this solution. For example, 0.20 mL of this solution whencast on a 1′×1′ glass plate, gave a ˜24 μm thick coating. The glassplate was placed on a horizontal support surface, and the solution wasevenly casted on the glass plate. Around 10 min were allowed to pass toallow most of the solvent to evaporate. To more fully evaporate thesolvent(s) and cure the film, the coated glass plate was put into adrying cabinet and heated to 150° C. for 24 hours.

After curing was complete, the PEO modified polyurethane coatings on thesubstrate appeared glossy and totally transparent. When tilting thecoated glass plate, oil (hexadecane, ˜0.02 mL) and water (˜0.05 mL)droplets slid off the coated area. Qualitatively, we observed thefollowing liquid could slide off the coatings without leaving any trace:ethanol, methanol, dodecane, DMF, diiodomethane. The coatings werestrong enough to resist scratching by a fingernail. After storage atroom temperature for approximately two days, the performance ofanti-smudge properties of PEO₂₀₀₀ and PEO₅₀₀₀ modified coatingsdegraded. However, the anti-smudge performance was regenerated when thesamples were slightly heated (˜50° C.) for 20 seconds,

Example 42 Preparation of PDMS Modified Polyurethane Coating UsingPolyol-alt-PIB

In preliminary studies, PDMS Modified Polyurethane Coating UsingPolyol-alt-PIB was prepared using the following procedure. Thispreparation has not been optimized. To obtain PIB modified polyurethanecoatings, the following three ingredients were combined and dissolved intoluene (2.0 mL):

-   -   (i) Polyol-alt-PIB (10 mg, see previous Example);    -   (ii) a poly(hexamethylene diisocyanate) (predominantly trimer,        65 mg, 80 wt % in butyl acetate, such as those sold under the        trademarks UH80-ULTRA SYSTEM® by SHERWIN-WILLIAMS Co.); and    -   (iii) polyol (100 mg, containing 32 wt % HEMA).

Different thickness of coating could be achieved by casting differentamount of this solution. For example, 0.20 mL of this solution when caston a 1′×1′ glass plate, gave a ˜29 μm thick coating. The glass plate wasput on a horizontal support surface, and the solution was evenly castedon the glass plate. Around 10 min were allowed to pass to allow most ofthe solvent to evaporate. To more fully evaporate the solvent(s) andcure the film, the coated glass plate was put into a drying cabinet andheated to 160° C. for 48 hours.

After curing was complete, the PIB modified polyurethane coating on thesubstrate appeared glossy and generally clear. When tilting the coatedglass plate, oil (hexadecane, ˜0.02 mL) and water (˜0.05 mL) dropletsslid off the coated area. The following liquids could slide off thecoatings without leaving any trace: ethanol, methanol, dodecane, DMF,and diiodomethane. The coatings were strong enough to resist scratchingby a fingernail.

Example 43 Preparation of PDMS Modified Polyurethane Coating UsingPEI-g-PDMS or P(S-alt-MA)-g-PDMS or PDMS-b-PGMA

In previous example, PDMS was reacted with polyol, and then the productof that reaction was reacted with polyisocyanate. In this example, PDMSwas reacted with polymers bearing functional groups, and that productwas then added to polyol and polyisocyanate either all at once or in anyorder. Because of the ease of synthesis this alternative “additive”method is described herein. Conveniently, such an additive can be usedwith a variety of polyols and polyisocyanates formulations.

To obtain a polyurethane coating with ˜4 wt % of PDMS, the followingcomponents were dissolved in chloroform or butanone (2.0 mL) to form areaction mixture: PEI-g-PDMS (or alternatively another such additive,for example, P(S-alt-MA)-g-PDMS or PDMS-b-PGMA) (45 mg) and apoly(hexamethylene diisocyanate) (320 mg, 80 wt % in butyl acetate). Thereaction mixture was heated to 60° C. for 1 h. [Poly(hexamethylenediisocyanate (predominantly trimer) is sold under the trademarksUH80-ULTRA SYSTEM® by SHERWIN-WILLIAMS Co.] Although not wishing to bebound by theory, it is believed that in this reaction amine/iminemoieties on PEI-g-PDMS (or carboxyl/anhydride moieties on P(S-alt-MA) orepoxide on PDMS-b-PGMA) reacted with poly(hexamethylene diisocyanate),and formed chains that have poly(hexamethylene diisocyanate) sidechains. Following the 1 h of heating to 60° C., polyol (450 mg,containing 32 wt % HEMA) and DMF (0.4 mL) were added into the reactionmixture. Coatings were then obtained by casting this mixture. Coatingsof different thicknesses could be achieved by casting different amountsof this solution. For example, 0.10 mL of this solution was cast on a1′×1′ glass plate resulting in a coating that was approximately 37 umthick. The 1′×1′ glass plate was placed on a horizontal surface, and thesolution was evenly casted on the glass plate. Around 10 min was allowedto pass so that most of the solvent could evaporate. To fully evaporatethe solvent(s) and cure the film, the coated glass plate was then placedinto a drying cabinet and heated to 120° C. for 12 hours.

After the coating was fully cured, the PDMS modified-polyurethanecoating on the glass substrate was glossy and transparent. A ˜37 umthick coating with ˜4 wt % of PDMS exhibited a transmittance of 99.1%.When tilting the coated glass plate, both hexadecane (˜0.02 mL) dropletsand water (˜0.05 mL) droplets rolled off the coated area easily. Thecoating was strong enough to resist a fingernail scratch. See Table 20for contact angle and sliding angle information.

Example 44 Preparation of Polybutadiene Modified Polyurethane CoatingUsing Polyol-g-Polybutadiene

Polybutadiene-g-polyol (5 mg), polyol (17 mg), and HDID (12 mg) wereplaced into a glass vial and THF (2.2 mL) was added. After dissolution,the resultant solution was drop cast onto a clean glass surface. After30 min of drying at room temperature, the coated glass was placed in anoven at 180° C. for 12 h to fully cure. A clear coating was obtained.Anti-smudge marker test and amphiphobic droplet sliding tests wereconducted and showed that this coating was amphiphobic and smudge proof.

Example 45 Rust Proof Test of PDMS Modified Epoxy Coating on Metal

PDMS modified Epoxy was prepared as mentioned in Example 40. It wasselectively coated on regions on a 10 cm×15 cm cast iron plate using thesame method as Example 40. The coated iron plate was cured in an oven at120° C. for 12 h. Then it was placed into a fresh water lake for oneweek. After this immersion week, uncoated regions appeared rusted whilecoated regions did not show any rust.

Example 46 Anti-Graffiti Test

FIGS. 24A-D show anti-graffiti properties of PEI-g-PDMS modified epoxycoatings containing 4.0 wt % PDMS comparing with unmodified epoxycoatings. Paints used included two commercially available oil-basedpaints that listed acetone, toluene, propane, butane, ethyl3-ethoxypropionate, dimethyl carbonate as their solvent, according totheir manual. All the modified and unmodified coated glass slides foruse in the test were placed vertically and were sprayed with a similaramount of the paints. On modified coatings, the spray paints could notstick well and shrank into small patches or were dragged to the bottomby gravity. In contrast, the spray paints fully covered the unmodifiedcoatings. The results show the potential of the modified coatingsdescribed herein for anti-graffiti applications.

FIGS. 24E-G show that PEI-g-PDMS modification introduces ink repellency.When a black permanent marker was dragged across the coatings, a uniformdark pattern was left on the unmodified sample (FIG. 24E). In thecontrast, the ink on the modified coating contracted into a faint patchytrace (FIG. 24F). Moreover, the patchy trace was readily removed by onewipe with a tissue after the ink dried (FIG. 24G). The black ink on theunmodified sample could not be wiped off in this way. PEI-g-PDMSmodified coating inhibited ink deposition and facilitated ink removal.The results show the potential of the modified coatings described hereinfor anti-graffiti applications.

A coating sample containing 7.4 wt % PDMS was prepared (using the firstprocedure wherein there was no additional hardener used) and applied toglass plates and was cured. The coated surface was then rubbed with acotton-fabric-wrapped probe under the pressure of 5.8×10³ Pa for 18.0hours at 40 rpm for a total 4.32×10⁴ cycles. After rubbing, the staticcontact angles of water and hexadecane droplets (5 μL) decreased from(101±1°) and (35±2°) to (100±1°) and (33±3°). After the rubbing test,the coating still exhibited good ink repellency (FIG. 24H).

All publications listed and cited herein are incorporated herein byreference in their entirety. It will be understood by those skilled inthe art that this description is made with reference to certainpreferred embodiments and that it is possible to make other embodimentsemploying the principles of the invention which fall within its spiritand scope as defined by the claims.

TABLE 1 List of the Example 1A copolymers Grafting density PFPE- (% OHcapped by Polymer P1 C(O)Cl PFPE) Example 0.20 g (0.72 mmol - 0.23 g(0.12 mmol) 13.6% 1A (i) OH groups) Example 0.20 g (0.72 mmol) 0.35 g(0.14 mmol) 16.5% 1A (ii) Example 0.60 g (2.2 mmol)  1.5 g (0.61 mmol)23.0% 1A (iii) Example 0.60 g (2.2 mmol)  1.7 g (0.72 mmol) 27.0% 1A(iv) Example 0.60 g (2.2 mmol)  2.2 g (0.93 mmol) 35.0% 1A (v)

TABLE 2 List of P(TFEMA_(x)-co-HEMA_(y)) copolymers Molar feed ratioPTFEMA)_(x):PHEMA_(y) EBrIB/FTEMA/HEMA-TMS/ Polymer (TFEMA:HEMA)(purified block ratios) Bipyridine/CuCl (mmol) P(TFEMA:co-HEMA) 1.0:1.00.98:1.0  0.510/13.5/13.5/1.56/0.550 (1) P(TFEMA-co-HEMA) 0.4:0.60.4:0.6 0.110/3.06/4.60/1.56/0.550 (2) P(TFEMA-co-HEMA) 0.3:0.70.30:0.73 0.101/1.95/4.60/0.300/0.100 (3)

TABLE 3 List of P(TFEMA-co-HEMA)-g-PFPE (Example 1B) copolymers GraftingP(TFEMA-co- density Polymer HEMA) (1) PFPE-C(O)Cl (theoretical) Example1B (i) 300 mg (1.00 mmol 0.24 g (0.10 mmol) 10% of OH) Example 1B 500 mg(1.68 mmol 0.65 g (0.27 mmol) 16% (ii) of OH) Example 500 mg (1.68 mmol0.97 g (0.39 mmol) 24% 1B (iii) of OH) Example 500 mg (1.7 mmol  1.3 g(0.52 mmol) 32% 1B (iv) of OH)

TABLE 4 List of the Example 1C copolymers PDMS Grafting density (% of OHcapped PDMS- with Polymer P1 O₂C₂(O)Cl PDMS) Example 1C (i) 0.42 g (1.5mmol) 0.77 g (0.168 mmol) 11.2% Example 1C (ii) 0.28 g (1.0 mmol) 0.64 g(0.14 mmol) 14.0% Example 1C (iii) 0.20 g (0.72 mmol) 0.64 g (0.14 mmol)19.4%

TABLE 5 Preparation of Example 1D (i) and Example 1D (ii) Acetic PolymerPrecursor Polymer anhydride Example 1D (i) 80 mg Example 1A (iii) 0.3 mL(2.3 mmol) Example 1D (ii) 36 mg Example 1C (ii) 0.3 mL (2.3 mmol)

TABLE 6 Formulation and properties of unmodified PU coating NCO WaterHexadecane % T Sample (moles) P1 Solvent NCO/OH (SA) (SA, °) Conc.Unmodified 7.0 mg 30.0 mg, 1.3 mL .033/.029 = 60 (25 μL) Wet 98.5% PU(0.033 mmol (0.029 mmol THF 1.13 (28.0 mg/mL) of of NCO) OH) SA—slidingangles.

TABLE 7 List of the coating formulations, and their respectiveproperties of the Example 1A PU-based films Hexadecane % T Example (SA,and Polymer NCO P1 1A NCO/OH Water (SA) 5 μL) (Conc). Example 3.0 mg 6.0mg 5.0 mg 0.014/0.011 = 56°, 25 μL (65°, 47° (47°) 85% 1A(i) (0.014mmol) (0.0058 mmol) (0.0058 mmol) 1.27 25 μL) (13.4 mg/mL) 3.7 mg 4.59.0 mg 0.017/0.015 = 30° (25 μL) 52° 

96% (0.017) (0.0042) (0.010 mmol) 1.2

(17 mg/mL) Example 2.5 mg 3.0 mg 6.0 mg 0.012/0.0090 = 49°, 20 μL 42°(42°) 85% 1A(ii) (0.012 mmol) (0.0029 mmol) (0.0060 mmol) 1.33 (75°, 20μL) (11.5 mg/mL) 4.6 mg 5.5 mg 11.7 mg 0.022/0.017 = 59° (15 μL), 58° 

92% (0.022 mmol) (0.0053 mmol) (0.015 mmol) 1.2

 μL) (21.7 mg/mL) Example 5.0 mg 7.3 mg 10 mg 0.023/0.016 = 69°, 20 μL26° (27°) 46% 1A(iii) (0.024 mmol) (0.0071 mmol) (0.0094 mmol) 1.43(84°, 20 μL) (33 mg/mL) 6.0 mg 14.6 mg 10 mg 0.028/0.022 = 85°, 20 μL38° (42°) 72% (0.028 mmol) (0.014 mmol) (0.0094 mmol) 1.27 (52°, 25 μL)(33 mg/mL) Example 3.5 mg 7.3 mg 10 mg 0.0164/0.014 = 62°, 20 μL, 25°32% 1A(iv) (0.016 mmol) (0.0070 mmol) (0.0074 mmol) 1.17 (NA°) (NA°) (19mg/mL) 5.00 mg 14.6 mg 10 mg .0235/0.0217 = 52°, 20 μL 33° (39°) 46%(0.0235 mmol) (0.0142 mmol) (0.0074 mmol) 1.08 (NA° for 25 μL) (24mg/mL) Example 3.3 mg 7.3 mg 10 mg .0154/0.013 = 68° (15 μL) 35° 8%1A(v) (0.015 mmol) (.0070) (0.0060 mmol) 1.18 (NA°) (NA°) (31 mg/mL) 4.9mg 14.6 mg 10 mg .023/.022 = 78° (15 μL) 38° 18% (0.023 mmol) (.0142mmol) (0.0060 mmol) 1.04 (NA°) (NA°) (39.3 mg/mL) Values shown in boldrepresent samples heated at 40° C. for 25 min before they were cast.Rubbing tests were performed for 60 min at 40 rpm, under a 400 g weight.(Note: The samples shown in italics were rubbed for 120 at 40 rpm, undera 400 g weight. SA denotes sliding angles. Sliding angles before rubbingtest are shown in (°) in regular font, while those recorded after therubbing test are shown in bold (°). NA - surface wet by the liquid andno sliding angles could be measured.

TABLE 8 List of coating formulations and resultant properties of the FPUfilms prepared from P(TFEMA-co-HEMA)-g-PFPE see Example 1B(i), Example1B(ii), Example 1B(iii), Example 1B(iv) P(TFEMA- Hexadecane NCOco-HEMA)- Water (SA, °, Polymer (moles) P1 g-PFPE NCO/OH (SA, °) 5 μL) %T (Conc.) Example 2.75 mg 5.0 mg 5.5 mg 0.013/0.012 = 48, 20 μL 48 (49°)85% (11.75 mg/mL) 1B(i) (0.0129 mmol) (0.0049 mmol) (0.0070 mmol) 1.09(61, 25 μL) 2.4 mg 3.0 mg 5.5 mg 0.013/0.01 = 54 (20 μL), 47 (47°) 87%(10.25 mg/mL) (0.011 mmol) (0.003 mmol) (0.0070 mmol) 1.34 (59, 25 μL)4.0 mg 4.3 mg 8.5 mg 0.019/0.012 = 80 (20 μL), 52 

94% (17 mg/mL) (0.019 mmol) (0.0041 mmol) (0.0085 mmol) 1.49

μL Example 5.4 mg 7.4 mg 16 mg 0.025/0.019 = 60, 20 μL 45 (49) 55% (46mg/mL) 1B(ii) (0.025 mmol) (0.0071 mmol) (0.012 mmol) 1.26 (62, 25 μL)

72, 20 μL, 49 

(85,

20 μL) 9.2 mg 14.6 24 mg 0.043/0.043 = 62, 20 μL 46 (49) 46% (35.8mg/mL) (0.043) (0.0143 mmol) (0.029 mmol) 1.0 (68, 25 μL) 11 mg 14.6 mg24 mg 0.052/0.043 = 78, 20 μL 46 (47) 48% (37 mg/mL) (0.052 mmol)(0.0143 mmol) (0.029 mmol) 1.2 (57, 25 μL) 11.0 mg 22.6 mg 24 mg0.0517/0.0503 = 76, 20 μL 49 (55) 61% (39.7) (0.0517 mmol) (0.0213)(0.029 mmol) 1.03 (72, mmol) 25 μL) Example 9.2 mg 14.6 mg 24 mg0.0432/0.035 = 70, 20 μL 44 (NA) 31% (35.5 mg/mL) 1B(iii) (0.043)(0.0143 mmol) (0.021 mmol) 1.22 (NA) 11 mg 14.6 mg 24 mg 0.0517/0.035 =88, 20 μL 51 (70) 32% (36.5 mg/mL) (0.052 mmol) (0.0143 mmol) (0.021mmol) 1.46 (57 25 μL) 11 mg 22.6 mg 24 mg 0.052/0.042 = 81, 20 μL 47(67) 44% (38 mg/mL) (0.052 mmol) (0.0213) (0.021 mmol) 1.22 (69, mmol)25 μL) Example 6.2 mg 147.6 mg 24 mg 0.029/0.029 = 40°, 15 μL 32° (NA)12% (34.7 mg/mL) 1B(iv) (0.029 mmol) (0.0147 mmol) (0.015 mmol) 1.0 (NA)8.0 mg 14.5 mg 24 mg 0.0376/0.029 = 55°, 20 μL 33° 14% (35.8 mg/mL)(0.037 mmol) (0.0140) (0.015 mmol) 1.29 (NA) (NA) 8.0 mg 22.5 mg 24 mg0.038/0.037 = 45°, 20 μL 32° 19% (39 mg/mL) (0.037 mmol) (0.0218 mmol)(0.015 mmol) 1.02 (NA) (NA) Reagents shown in bold represent samplesheated at 40° C. for 25 min before casting. Rubbing tests were performedfor 60 min at 40 rpm, using a 400 g weight. (Note: Samples shown initalics were rubbed for 120 min at 40 rpm, using a 400 g weight).Sliding angles (SAs) observed before the rubbing tests are shown in (°)while those observed after the rubbing tests are shown in bold (°). NAindicates that the surface had become wet by the liquid and no slidingangles could be measured.

TABLE 9 Formulations of the Example 1C copolymers THF:AcN Polymer NCO P1Example 1C NCO/OH (v/v) Conc. Example 1C(i) A 14.5 mg 26.2 mg 17.5 mg0.068/0.0474 = 1:4 ~23.2 mg/mL  (0.0680 mmol) (0.0254 mmol) (0.0220mmol) 1.44 Example 1C(ii) A 10 mg 21 mg 14 mg 0.047/0.0364 = 1:4 22.5mg/mL (0.047) (0.0204 mmol) (0.015 mmol) 1.3 B 5.6 mg 20 mg 5.5 mg.026/.025 = 1:1 34.5 mg/mL (0.026 mmol) (0.019 mmol) (0.0057 mmol) 1.05Example 1C(iii) A 10 mg 21 mg 16 mg 0.047/0.033 = 1:4 23.5 mg/mL (0.047mmol) (0.020 mmol) (0.013 mmol) 1.42 B 10 mg 40 mg 8.25 mg 0.047/0.045 =1.1:1   52.9 mg/mL (0.047 mmol) (0.039 mmol) (0.00640 mmol) 1.04

TABLE 10 Properties of Example 1C Copolymer-Based PU films Spin coatingProperties Drop casting (A) Spin coating (A) Drop casting (B) (B)Example 1C (i) — — Water (SA) 40° (15 μL) (60°, 78° (20 μL), (56, — — 15μL) 25 μL) Hexadecane (SA, 3-5° (6-8°) 18° (elongated — — 5 μL) drop)(21° tailing) % Transmittance 92-96% 98% — — Anti-Ink Good Good — —Example 1C (ii) — — — — Water (SA) — 80° (20 μL) 81° (20 μL) (60, 85°(20 μL) (54°, 25 μL) 25 μL) (NA) Hexadecane (SA) — ~35° (63° Wet 55°elongated (elongated droplets) droplets) (NA) Optical (% T) — 95% 4% 98%Anti-ink — Average Average Average Example 1C (iii) — Water (SA) — 40°(20 μL) 80° (20 μL) (46°, 75° (15 μL); (68°, 20 μL) 25 μL) (NA)Hexadecane (SA, 42° , NA 44° 5 μL) (NA) (elongated droplets) (NA)Optical Properties 98 8 98 (% T) Anti-Ink Average Average Average NA:indicates that the solvent spread on the film, so that it was impossibleto measure the SA. AcN denotes Acetonitrile Spin coating was performedat 2000 rpm, time 30 s, acceleration 500 rpm. Rubbing tests wereperformed for 60 min at 40 rpm using a 100 g weight. % T at a wavelengthof 500 nm. The sliding angle (SA) values in regular font represent theSAs (in °) measured before the rubbing tests, while the values in boldfont represent the SA measured (in °) after the rubbing test.

TABLE 11 Properties of the Example 1D (i) Based Films Spin Coating SpinCoating (two Properties Drop casting (single layer) layers) Water (SA)75° (20 μL), (NA) 67° (20 μL), 65° (20 μL), (NA) (NA) Hexadecane 70° (5μL), (NA) 40° (5 μL), (NA) 38° (5 μL), (NA) Optical Clarity 15 87 85 (%T) Mechanical Film completely Film Film destroyed Durability destroyeddestroyed Spin coating conditions: 2000 rpm, 30 s duration, accelerationof 500 rpm. % T at a wavelength of 500 nm. Rubbing test: 20 min at 40rpm using 250 g weight. NA indicates that the droplet either wet thesurface or did not slide. Sliding angles reported in bold representvalues observed after the rubbing test.

TABLE 12 Properties of the Example 1D (ii) Based PU Films PropertiesDrop casting Spin coating* Spin coating** Water (SA, °) 45° (15 μL) 35°(15 μL) 35° (15 μL) (NA) (NA) (NA) Hexadecane Wet the film 45° (small41° (small (SA, °) droplets left droplets left behind-Tailing)behind-Tailing) Optical 5.0 95 93 Properties (% T) Mechanical Filmdestroyed Film destroyed Film destroyed after Properties^(a) afterrubbing after rubbing rubbing Spin coating conditions: 2000 rpm, 30 sduration, acceleration of 500 rpm. *represents a single layer preparedvia spin coating. **Represents two layers prepared via spin coating. % Tobserved at a wavelength of 500 nm. ^(a)Films were lost after they weresubjected to rubbing for 20 min at 40 rpm using a 250 g weight.

TABLE 13 Preparation of FPU films from Example 2A Example Sample NCO P12A NCO/OH PFPE (wt %) Conc./solvent 5A 2.0 mg 5.0 mg 2.1 mg0.0094/0.0083 = 1.09 mg/9.1 mg = 7.9 mg/mL in (0.0094 mmol (0.0049 mmol(0.0034) 1.3 11.9% THE of of NCO) OH) 58 2.8 mg 10 mg 2.1 mg 0.013/0.013= 1.09/14.9 mg = 12.4 mg/mL (0.013 mmol (0.0097 mmol (0.0034) 1.01 7.3%in THF of of NCO) OH)

TABLE 14 Properties of FPU films based on Example 2A Properties 5-A 5-BWater (SA) 70° , 15 μL, (55°, 75°, 15 μL, (73°, 20 μL) 20 μL) Hexadecane(SA, 5 μL) 45° (52) 45° (62) Optical Clarity 40% 46% MechanicalDurability^(a) Stable Stable SA (sliding angles), ^(a)20 min at 250 g at40 rpm. Values in the bold parenthesis denote sliding angles measuredafter the rubbing test.

TABLE 15 Formulations Employed for the Preparation of the Example 2BBased PU Films Example Conc. Sample NCO P1 2B NCO/OH PDMS (wt. %)(mg/mL) 6-A 44 mg 114 mg 28 mg 0.21/0.12 = 1.4 18.9/186 = 10.1 12.4(0.21 mmol) (0.110 mmol) (0.037 mmol) 6-B 11.5 mg 32 mg 12.2 mg0.054/0.048 = 8.54/55.7 = 15.2 13.9 (0.0540 mmol) (0.031 mmol) (0.0170mmol) 1.13

TABLE 16 Properties of the Example 2B Based PU Films 6-B- 6-A-Drop6-A-Spin Drop 6-B-Spin Properties casting coating casting Coating Water(20 μL) 24° (31°)^(a) 28° (46°)^(a) 23° (45°)^(a) 25° (67°)^(a) SAHexadecane (5 μL) 10° (12°)^(a) 10° (15°)^(a)  7° (23°)^(a)  7°(31°)^(a) SA Optical Clarity 85.5 99.7 68.0 99.0 (% T)^(b)Ink-Resistance Good* Good* Good* Good* Spin coating: 2000 rpm, time 30s, acceleration 500, SA (Sliding angle, °). ^(a)Rubbing tests wereperformed under a 250 g load at 40 rpm, for 60 min. ^(b)% Transmittancerecorded at 500 nm. *Good-resistance to permanent ink marker.

TABLE 17 Formulations for Silica Particle-Embedded Example 1A(i) PUFilms Mass of FPU Hexadecane Water Mass of the (mg) at (staticHexadecane (static Water silica particles 9.2 wt. of contact (slidingcontact (sliding Sample (mg) F % angle) angle) angle) angle) 1 20(uncoated) 20 65°  88°* 102° 70° 2 40 (coated) 20 68° 44° 106° 33° 3 30(coated) 20 71° 55° 113° 45° 4 46 (coated) 20 65° 60° (for 10 μL) 121°78° Note. The volumes of the water and hexadecane droplets were 20 and 5μL, respectively, except where mentioned. *Represents sample have someweak spots where hexadecane pinned to the surface. Note example 1A(i)was used for PU modification.

TABLE 18 Properties of Example PEI-g-PDMS modified PU Films (Example 43)Water Contact Hexadecane Water Sliding Hexadecane PDMS Angle ContactAngle Sliding wt % (5 μL) Angle (5 μL) (15 μL) Angle (5 μL) 4% 102.3°33.4° 38° 5°   8% 102.5° 33.7° 34° 4.5°

TABLE 19 Types of P20 and amounts that were mixed with Bis-A (0.10 mL,containing 0.68 mmol glycidyl groups) in chloroform (0.50 mL) (seeExample 39A) Amount Ideal Epoxide Consuming P20 (in mg) (in mmol) P20-115.0 0.085~0.232 P20-2 15.0 0.042~0.116 P20-3 15.0 0.016~0.032 P20-415.0 0.010 P20-5 15.0 0.018~0.036 P20-6 15.0 0.018~0.036 P20-7 15.00.035 P20-8 15.0 0.085~0.232

TABLE 20 Liquid static contact angle and sliding angle of PDMS modifiedepoxy films Miscible Surface tension Contact Sliding with @ 20° C. AngleAngle Liquid PDMS? in mN/m* (5 μL) (5 μL) Diiodomethane Yes 50.80 67 ±1° 9° Hexadecane Yes 27.47 35 ± 2° 5° THF Yes 26.40 26 ± 2° 5° DodecaneYes 25.35 26 ± 2° 5° Decane Yes 23.83 18 ± 1° 5° Octane Yes 21.62 Theliquid spread on the Polydimethyl Yes 19.00 surface, and did not slide.siloxane Hexane Yes 18.43 Water No 72.80 101 ± 1°  60° (15 μL) DMF No37.10 50 ± 4° 41°  Methanol No 22.70 29 ± 2° 11°  Ethanol No 22.10 28 ±1° 10°  Perfluorooctane No 14.00  2 ± 1° 1° *Surface tension dataobtained from http://www.surface-tension.de/. Note: surface tension unitof millinewtons per meter (mN · m−1) is equivalent to dynes percentimetre.

We claim:
 1. A coating composition prepared by combining: a graftcopolymer that is a polyol, polyamine, polyimine, poly(carboxylic acid),or polyanhydride that comprises a polysiloxane, PFPE, PEO, PIB, or PBmoiety; di-, tri-, or poly-isocyanate; and, optionally a polyol,polyamine, polyimine, poly(carboxylic acid), and/or polyanhydride thatdoes not comprise a polysiloxane, PFPE, PEO, PIB, nor PB moiety; whereinthe coating composition comprises about 0.1wt % to about 40 wt %siloxane, fluorine, PEO, PIB, or PB.
 2. The coating composition of claim1, wherein the polyol that comprises a polysiloxane, PFPE, PEO, PIB, orPB moiety is Polyol-g-PIB.
 3. The coating composition of claim 1,wherein the polyanhydride that comprises a polysiloxane, PFPE, PEO, PIB,or PB moiety is P(S-alt-MA)-g-PEO .
 4. A coating composition prepared bycombining: a graft copolymer comprising at least one functional moietyand at least one polysiloxane or PFPE moiety; isocyanate (bi-, tri- ormulti-); and polyol, polyamine, or a combination of polyol andpolyamine; wherein a coating resulting from application of the coatingcomposition is anti-smudge.
 5. A coating composition prepared bycombining: a graft copolymer comprising at least one functional moietyand at least one poly (ethylene glycol) methyl ether (“PEO”),polyisobutylene (“PIB”), or polybutadiene (“PB”) moiety; isocyanate(bi-, tri- or multi-); and polyol, polyamine, or a combination of polyoland polyamine; wherein a coating resulting from application of thecoating composition is anti-smudge.
 6. The coating composition of claim4, wherein the coating is clear.
 7. The coating composition of claim 5,wherein the coating is clear.
 8. The coating composition of claim 4,wherein the polymer and the isocyanate are allowed to react and then thepolyol, polyamine, or combination of polyol and polyamine is added. 9.The coating composition claim 5, wherein the polymer and the isocyanateare allowed to react and then the polyol, polyamine, or a combination ofpolyol and polyamine is added.